Method and apparatus for applying electrical charge through a fluid with a sinusoidal waveform having at step discontinuity

ABSTRACT

An apparatus and method are provided, wherein the apparatus includes an electrode and a control circuit. The electrode lacks a corresponding return electrode of opposite polarity on the apparatus. The control circuit is electrically coupled to the electrode and configured to generate and apply to the electrode a voltage having a sinusoidal waveform having at least one step on an edge of the waveform, wherein each step comprises a local peak. The apparatus is arranged to generate an alternating electric field between the electrode and a surface or volume of space in response to the applied voltage.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application is a continuation of U.S. patent applicationSer. No. 12/639,622, filed Dec. 16, 2009, which is based on and claimsthe benefit of U.S. Provisional Patent Application No. 61/138,465, filedDec. 17, 2008, and U.S. Provisional Patent Application No. 61/248,557,filed Oct. 5, 2009, the contents of all cross-referenced applicationsare hereby incorporated by reference in their entireties.

FIELD OF THE DISCLOSURE

The present disclosure relates to deactivating or destroyingmicroorganisms by a mechanism such as electroporation and/orelectrohydraulic shock. In one particular example, the disclosurerelates to applying an electrical potential to the microorganismsthrough a liquid delivered by an apparatus, such as for example anapparatus producing an electrochemically-activated liquid with anelectrolysis cell.

BACKGROUND

Electrolysis cells are used in a variety of different applications forchanging one or more characteristics of a fluid. For example,electrolysis cells have been used in cleaning/sanitizing applications,medical industries, and semiconductor manufacturing processes.Electrolysis cells have also been used in a variety of otherapplications and have had different configurations.

For cleaning/sanitizing applications, electrolysis cells are used tocreate anolyte electrochemically activated (EA) liquid and catholyte EAliquid. Anolyte EA liquids have known sanitizing properties, andcatholyte EA liquids have known cleaning properties. Examples ofcleaning and/or sanitizing systems are disclosed in Field et al. U.S.Publication No. 2007/0186368 A1, published Aug. 16, 2007.

However, the sanitizing capabilities of anolyte EA liquids can belimited in some applications. An aspect, among others, of the presentapplication is directed to improved methods, systems and/or apparatusfor enhancing sanitizing properties of a liquid.

SUMMARY

An aspect of the disclosure for example relates to an apparatus havingan electrode and a control circuit. The electrode lacks a correspondingreturn electrode of opposite polarity on the apparatus. The controlcircuit is electrically coupled to the electrode and configured togenerate and apply to the electrode a voltage having a sinusoidalwaveform having at least one step on an edge of the waveform, whereineach step comprises a local peak. The apparatus is arranged to generatean alternating electric field between the electrode and a surface orvolume of space in response to the applied voltage.

Another aspect of the disclosure for example relates to an apparatusincluding a liquid flow path, a liquid dispenser coupled in the liquidflow path and an electrode electrically coupled to the liquid flow path,which lacks a corresponding return electrode representing a circuitground for the electrode on the apparatus. A control circuit is coupledto the electrode and is configured to generate and apply to theelectrode a voltage having a sinusoidal waveform comprising at least onestep on an edge of the waveform, wherein each step comprises a localpeak.

Another aspect of the disclosure for example relates to a method. Themethod includes: applying a voltage to an electrode on an apparatus, thevoltage having a sinusoidal waveform having at least one step on an edgeof the waveform, wherein each step comprises a local peak; and arrangingthe apparatus to generate an alternating electric field between theelectrode and a surface or volume of space in response to the appliedvoltage, wherein the apparatus lacks a corresponding return electroderepresenting a circuit ground for the electrode on the apparatus.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a simplified, schematic diagram of an example of a hand-heldspray bottle according to an exemplary aspect of the present disclosure.

FIG. 2 illustrates an example of an electrolysis cell having anion-selective membrane.

FIG. 3 illustrates an electrolysis cell having no ion-selective membraneaccording to a further example of the disclosure.

FIGS. 4A-4D are diagrams illustrating an example of a dirt cleaningmechanism performed by a liquid that is electrochemically-activatedaccording to an aspect of the disclosure.

FIG. 5 illustrates an example of an electrolysis cell having a tubularshape according to an illustrative example.

FIG. 6 is an exploded, perspective view of an electroporation electrodeaccording to an illustrative example of the disclosure.

FIG. 7A is a diagram illustrating an example of conductive paths formedbetween a spray head and a surface by an electrically charged outputspray.

FIG. 7B is a diagram illustrating an example of an electroporationmechanism, whereby a cell suspended in a medium is subjected to anelectric field.

FIG. 7C is a diagram illustrating an example of a cell membrane havingpores expanded by electroporation.

FIG. 8 is a diagram illustrating an example of a spray bottle sprayingan electrically charged liquid to a surface.

FIG. 9 is a diagram illustrating an example of a surface being sprayedand wetted with an electrically charged liquid.

FIG. 10A is a perspective view of a hand-held spray bottle according toan embodiment of the disclosure.

FIG. 10B is a perspective view of an exposed left-half of the hand-heldspray bottle according to an embodiment of the disclosure.

FIG. 10C is a side view of an exposed spray head of the hand-held spraybottle according to an embodiment of the disclosure.

FIG. 11 is a waveform diagram illustrating an example of the voltagepattern applied to the anode and cathode of an electrolysis cell in thespray bottle according to an exemplary aspect of the present disclosure.

FIG. 12 is a block diagram of an example of a control circuit forcontrolling the electrolysis cell on the spray bottle according to anexemplary aspect of the disclosure.

FIG. 13A is an example of a waveform diagram illustrating the voltagepattern applied to an electroporation electrode in the spray bottleaccording to an exemplary aspect of the present disclosure.

FIG. 13B is an example of a waveform diagram illustrating a frequencypattern applied to an electroporation electrode in the spray bottleaccording to an exemplary aspect of the present disclosure.

FIG. 13C is an example of a waveform diagram illustrating a frequencypattern applied to an electroporation electrode in the spray bottleaccording to an exemplary aspect of the present disclosure.

FIG. 14 is a block diagram of an example of a control circuit forcontrolling the electroporation electrode on the spray bottle accordingto an exemplary aspect of the disclosure.

FIG. 15 is a perspective view of an example of a mobile floor cleaningmachine according to another embodiment of the disclosure.

FIG. 16 is a perspective view of an example of an all-surface cleaneraccording to another embodiment of the disclosure.

FIG. 17 is a diagram illustrating an example of a flat mop embodiment,which includes at least one electrolysis cell and/or at least oneelectroporation electrode, such as those described in the presentdisclosure.

FIG. 18 is a diagram illustrating an example device, which can bestationary or movable relative to a surface.

FIG. 19 is a block diagram, which illustrates a system according to anexample embodiment of the disclosure, which can be incorporated into anyof the embodiments disclosed herein, for example.

FIGS. 20A and 20B are graphs, which plot examples of the potential fieldand electric field, respectively, as a function of distance from thenozzle for the embodiment shown in FIGS. 5-6 and 10-14, for example.

FIG. 21 is a diagram illustrating a system according to an exampleembodiment of the disclosure in which a suspension additive is added toa liquid dispensed from an apparatus to enhance suspension properties ofthe dispensed liquid.

FIG. 22 is a schematic illustration of a spray bottle configured toretain one or more liquid-activating materials for altering theoxidation-reduction potential (ORP) of liquids retained and dispensed bythe spray bottle, for example.

FIG. 23 is a schematic illustration of a cartridge containing aliquid-activating material, which may be installed in a fluid line of aflow-through system, for example.

DETAILED DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS

The following is provided as additional description of examples of oneor more aspects of the present disclosure. The below detaileddescription and above-referenced Figures should not to be read aslimiting or narrowing the scope of the invention as will be claimed inissued claims. It will be appreciated that other embodiments of theinvention covered by one or more of the claims may have structure andfunction which are different in one or more aspects from the figures andexamples discussed herein, and may embody different structures, methodsand/or combinations thereof of making or using the invention as claimedin the claims, for example.

Also, the following description is divided into sections with one ormore section headings. These sections and headings are provided for easeof reading only and, for example, do not limit one or more aspects ofthe disclosure discussed in a particular section and/or section headingwith respect to a particular example and/or embodiment from beingcombined with, applied to, and/or utilized in another particularexample, and/or embodiment which is described in another section and/orsection heading. Elements, features and other aspects of one or moreexamples may be combined and/or interchangeable with elements, featuresand other aspects of one or more other examples described herein.

An aspect of the present disclosure for example relates to enhancingsanitization properties of an output fluid (including a liquid streamand/or a gas/liquid mixture, water vapor, gaseous liquid, mist, spray oraerosol mixture for example) that is dispensed from an apparatus. In oneexample, the disclosure relates to enhancing sanitization properties ofan output liquid (including a liquid stream and/or a gas/liquid mixture,gaseous liquid, mist, spray or aerosol mixture for example). Anexemplary basis for sanitization in one or more examples of the presentdisclosure includes applying an electric field, such as an alternatingelectric field, to cells of a microorganism on a surface being treated,wherein the electric field meets or surpasses a threshold such that thecells become permanently damaged by a process known as irreversibleelectroporation, for example. If the electric field threshold is reachedor surpassed, electroporation will compromise the viability of thecells, resulting in irreversible electroporation.

In one or more examples, the microorganisms are suspended from thesurface by liquid dispensed from the apparatus and through which anelectric field is applied. Such suspension can be enhanced, for exampleby altering the oxidation-reduction potential of the liquid to exceedabout +/−50 milivolts, for example. Suspension of the microorganisms mayenhance application of the electric field to cells of the microorganism.

In a particular example, an aspect of the present disclosure relates toa method and apparatus for enhancing sanitization properties ofelectrolyzed liquids produced by an electrolysis cell carried by astationary or movable apparatus, such as a hand-held spray bottle ordevice, a mobile floor cleaner, a hand sanitizing station or device, afood sanitizer, fabric or dish washing machine, and/or other apparatusfor generating or applying a liquid and/or gas/liquid mixture to asurface or volume of space. The electrolysis cell can, for example,increase the ORP of a liquid to aid in suspension of the microorganismsthrough the action of charged nanobubbles, for example. Other mechanismscan also be used to alter a liquid's ORP and/or enhance suspension ofparticles and microorganisms from a surface.

Embodiments of the present disclosure can be used in a variety ofdifferent applications and housed in a variety of different types ofapparatus, including but not limited to apparatus that are hand-held,mobile, immobile, wall-mounted, motorized or non-motorized, wheeled ornon-wheeled, etc. In the following example, an electrolysis cell and anelectroporation electrode are incorporated in a hand-held spray bottle.It will be appreciated that one or more of the various aspects of one ormore of the examples discussed in the present disclosure may be combinedwith and/or substituted for other aspects in alternate embodiments asappropriate. The headings set out herein are utilized for convenienceand are not intended, for example, to limit aspects of an embodimentdiscussed under that to that or a particular embodiment or example.Also, for example, although the term “electroporation electrode” is usedin the description to refer to an electrode, this term is used forconvenience only and is not intended to limit its operation or effect onmicroorganisms to a process of electroporation.

In the one or more examples of the present disclosure, instead of usingtraditional electrical probes for example to deliver an applied electricfield, an apparatus may be configured to deliver such an appliedelectric field through a charged output liquid.

1. Hand-Held Spray Device Example

FIG. 1 is a simplified, schematic diagram of an example of a hand-heldspray device, here in the form of a hand-held spray bottle 10 accordingto an exemplary aspect of the present disclosure. In another example,the spray device may form part of a larger device or system. In theexample shown in FIG. 1, spray bottle 10 includes a reservoir 12 forcontaining a liquid to be treated and then dispensed through a nozzle14. In an example, the liquid to be treated includes an aqueouscomposition, such as regular tap water.

Spray bottle 10 further includes an inlet filter 16, one or moreelectrolysis cells 18, tubes 20 and 22, pump 24, actuator 26, switch 28,circuit board and control electronics 30 and batteries 32. Although notshown in FIG. 1, tubes 20 and 22 may be housed within a neck and barrel,respectively of bottle 10, for example. A cap seals reservoir 12 aroundthe neck of bottle 10. Batteries 32 can include disposable batteriesand/or rechargeable batteries, for example, or other appropriateportable or corded electrical source in addition to or in place ofbatteries, to provide electrical power to electrolysis cell 18 and pump24 when energized by circuit board and control electronics 30.

In the example shown in FIG. 1, actuator 26 is a trigger-style actuator,which actuates momentary switch 28 between open and closed states. Forexample, when the user squeezes the hand trigger, the trigger actuatesthe switch from the open state to the closed state. When the userreleases the hand trigger, the trigger actuates the switch into the openstate. However, actuator 26 can have other styles or structure inalternative embodiments and can be eliminated in further embodiments. Inembodiments that lack a separate actuator, switch 28 for example can beactuated directly by a user. When switch 28 is in the open,non-conducting state, control electronics 30 de-energizes electrolysiscell 18 and pump 24. When switch 28 is in the closed, conducting state,control electronics 30 energizes electrolysis cell 18 and pump 24. Pump24 draws liquid from reservoir 12 through filter 16, electrolysis cell18, and tube 20 and forces the liquid out tube 22 and nozzle 14.Depending on the sprayer, nozzle 14 may or may not be adjustable, so asto select between squirting a stream, aerosolizing a mist, or dispensinga spray, for example.

Switch 28, itself, can have any suitable actuator type, such as apush-button switch as shown in FIG. 1, a toggle, a rocker, anymechanical linkage, and/or any sensor to sense input, including forexample capacitive, resistive plastic, thermal, inductive, mechanical,non-mechanical, electro-mechanical, or other sensor, etc. Switch 28 canhave any suitable contact arrangement, such as momenary, single-polesingle throw, etc.

In an alternative embodiment, pump 24 is replaced with a mechanicalpump, such as a hand-triggered positive displacement pump, whereinactuator trigger 26 acts directly on the pump by mechanical action. Inthis embodiment, switch 28 could be separately actuated from the pump24, such as a power switch, to energize electrolysis cell 18. In afurther embodiment, batteries 32 are eliminated and power is deliveredvia another portable source, e.g., a rotating dynamo, shaker or solarsource etc., or delivered to spray bottle 10 from an external source,such as through a power cord, plug, and/or contact terminals. Forexample, in an alternate embodiment a user may actuate an internaldynamo while squeezing the trigger in order to generate electricalpower. The spray bottle can comprise any suitable power source, such asa portable power source carried by the bottle or terminals carried bythe bottle for connecting to an external power source.

The arrangement shown in FIG. 1 is provided merely as a non-limitingexample. Spray bottle 10 can have any other structural and/or functionalarrangement. For example, pump 24 can be located downstream of cell 18,as shown in FIG. 1, or upstream of cell 18 with respect to the directionof fluid flow from reservoir 12 to nozzle 14. Spray bottle 10 may be anyother appropriate hand-held device for example, and need not be in theshape of a bottle, or spray bottle. Other form factors or ergonomicshapes for example may be utilized in other embodiments. For example,the spray device may have the form of a wand, which may or may not beconnected to a cleaning device, such as a mop bucket, a motorized ornon-motorized all-purpose cleaner, a mobile cleaning device with orwithout a separate cleaning head, a vehicle, etc.

As described in more detail below, the spray bottle contains a liquid tobe sprayed on a surface or into a volume of space to be cleaned and/orsanitized. In one non-limiting example, electrolysis cell 18 convertsthe liquid to an anolyte EA liquid and a catholyte EA liquid prior tobeing dispensed from the nozzle 14 as an output spray (or stream, forexample). The anolyte and catholyte EA liquids can be dispensed as acombined mixture or as separate spray outputs, such as through separatetubes and/or nozzles. In the embodiment shown in FIG. 1, the anolyte andcatholyte EA liquids are dispensed as a combined mixture. With a smalland intermittent output flow rate provided the spray bottle,electrolysis cell 18 can have a small package and be powered bybatteries carried by the package or spray bottle, for example.

Spray bottle 10 can further include a separate electrical conductor,lead, or other electrical and/or electromagnetic component, for examplean electrode, e.g., high voltage electrode 35, which is positioned in,or in appropriate relation to, the liquid or liquid path to impart,induce or otherwise cause an electrical potential in the liquid outputspray relative to Earth ground, for example. If a liquid forming aliquid output spray, for instance, already carries a charge, such anelectrical potential can be a separate or additional electricalpotential in the liquid output spray, for example. In the example shownin FIG. 1, electrode 35 is positioned along tube 22 and is configured tomake electrical contact with the liquid flowing through the tube.However, electrode 35 can be located at any position along the liquidflow path from reservoir 12 to nozzle 14 (or even external to spraybottle 10) for example. Control circuit 30 energizes electrode 35 whentrigger 26 actuates switch 28 into the closed state, and de-energizeselectrode 35 when trigger 26 actuates switch 28 into the open state. Itwill be appreciated that other energizing, de-energizing states orpatterns could be used in other embodiments, such as de-energizingelectrode 35 even during part of the time trigger 26 is operated and/orliquid is being dispensed, for example. In this example, electrode 35has no corresponding return electrode of opposite polarity. Further, inother embodiments more than one electrical conductor, lead, or otherelectrical component or combination thereof could be utilized to impart,induce or otherwise cause an electrical potential.

Electrical potential created and/or supplemented by electrode 35 isapplied to microorganisms on the surface being cleaned through liquiddispensed and, if the charge delivery is of a sufficient magnitude, sucha charge can cause irreversible damage, destruction to or otherwiseeliminate microorganisms through a mechanism such as electroporationand/or elecrohydraulic shock, as discussed in examples in more detailbelow. This enhances sanitization properties of the liquid output sprayduring use.

2. Electrolysis Cells Example

An electrolysis cell includes any fluid treatment cell that is adaptedto apply an electric field across the fluid between at least one anodeelectrode and at least one cathode electrode. An electrolysis cell canhave any suitable number of electrodes, any suitable number of chambersfor containing the fluid, and any suitable number of fluid inputs andfluid outputs. The cell can be adapted to treat any fluid (such as aliquid or gas-liquid combination). The cell can include one or moreion-selective membranes between the anode and cathode or can beconfigured without any ion selective membranes. An electrolysis cellhaving an ion-selective membrane is referred to in this example as a“functional generator”. This term is not intended to limiting; it willbe appreciated that other appropriate device and/or structure mayqualify as a functional generator.

Electrolysis cells can be used in a variety of different applicationsand can have a variety of different structures, such as but not limitedto a spray bottle as discussed with reference to FIG. 1, and/or thestructures disclosed in Field et al. U.S. Patent Publication No.2007/0186368, published Aug. 16, 2007 and incorporated herein in itsentirety. Thus, although various elements and processes relating toelectrolysis are described herein relative to the context of a spraybottle, these elements and processes can be applied to, and incorporatedin, other, non-spray bottle applications.

2.1 Electrolysis Cell Having a Membrane Example

FIG. 2 is a schematic diagram illustrating an example of an electrolysiscell 50 that can be used in the spray bottle shown in FIG. 1, forexample. Electrolysis cell 50 receives liquid to be treated from aliquid source 52. Liquid source 52 can include a tank or other solutionreservoir, such as reservoir 12 in FIG. 1, or can include a fitting orother inlet for receiving a liquid from an external source.

Cell 50 has one or more anode chambers 54 and one or more cathodechambers 56 (known e.g. as reaction chambers), which are separated by anion exchange membrane 58, such as a cation (e.g., a proton exchangemembrane) or anion exchange membrane. One or more anode electrodes 60and cathode electrodes 62 (one of each electrode shown) are disposed ineach anode chamber 54 and each cathode chamber 56, respectively. Theanode and cathode electrodes 60, 62 can be made from any suitablematerial, for example stainless steel, a conductive polymer, titaniumand/or titanium coated with a precious metal, such as platinum, or anyother suitable electrode material. In one example, at least one of theanode and cathode is at least partially or wholly made from a conductivepolymer. The electrodes and respective chambers can have any suitableshape and construction. For example, the electrodes can be flat plates,coaxial plates, rods, or a combination thereof. Each electrode can have,for example, a solid construction or can have one or more apertures. Inone example, each electrode is formed as a mesh. In addition, multiplecells 50 can be coupled in series or in parallel with one another, forexample. The electrodes 60, 62 are electrically connected to oppositeterminals of a conventional power supply (not shown).

Ion exchange membrane 58 is located between electrodes 60 and 62. Theion exchange membrane 58 can include a cation exchange membrane (e.g., aproton exchange membrane) or an anion exchange membrane. Suitable cationexchange membranes for membrane 38 include partially and fullyfluorinated ionomers, polyaromatic ionomers, and combinations thereof.Examples of suitable commercially available ionomers for membrane 38include sulfonated tetrafluorethylene copolymers available under thetrademark “NAFION” from E.I. du Pont de Nemours and Company, Wilmington,Del.; perfluorinated carboxylic acid ionomers available under thetrademark “FLEMION” from Asahi Glass Co., Ltd., Japan; perfluorinatedsulfonic acid ionomers available under the trademark “ACIPLEX” Aciplexfrom Asahi Chemical Industries Co. Ltd., Japan; and combinationsthereof. Other examples of suitable membranes include, for example,those available from Membranes International Inc. of Glen Rock, N.J.,such as the CMI-70005 cation exchange membrane and the AMI-70015 anionexchange membrane. However, any ion exchange membrane can be used inother examples.

The power supply can provide a constant DC output voltage, a pulsed orotherwise modulated DC output voltage, and/or a pulsed or otherwisemodulated AC output voltage to the anode and cathode electrodes, forexample. The power supply can have any suitable output voltage level,current level, duty cycle or waveform, etc.

For example in one embodiment, the power supply applies the voltagesupplied to the plates at a relative steady state. The power supply(and/or control electronics) includes a DC/DC converter that uses apulse-width modulation (PWM) control scheme to control voltage andcurrent output. Other types of power supplies can also be used, whichcan be pulsed or not pulsed and at other voltage and power ranges. Theparameters may vary depending on a specific application and/orembodiment.

During operation, feed water (or other liquid to be treated) is suppliedfrom source 52 to both anode chamber 54 and cathode chamber 56. In thecase of a cation exchange membrane, upon application of a DC voltagepotential across anode 60 and cathode 62, such as a voltage in a rangeof about 5 Volts (V) to about 28V, or for example about 5V to about 38V,cations originally present in the anode chamber 54 move across theion-exchange membrane 58 towards cathode 62 while anions in anodechamber 54 move towards anode 60. However, anions present in cathodechamber 56 are not able to pass through the cation-exchange membrane,and therefore remain confined within cathode chamber 56.

As a result, cell 50 can electrochemically activate the feed water by atleast partially utilizing electrolysis and produceselectrochemically-activated water in the form of an acidic anolytecomposition 70 and a basic catholyte composition 72. In one example, theanolyte composition 70 has an oxidation-reduction potential (ORP) of atleast about +50 mV (e.g., in a range of +50 mV to +1200 mV), and thecatholyte composition 72 has an ORP of at least about −50 mV (e.g., in arange of −50 mV to −1000 mV).

If desired, the anolyte and catholyte can be generated in differentratios to one another through modifications to the structure of theelectrolysis cell, for example. For example, the cell can be configuredto produce a greater volume of catholyte than anolyte if the primaryfunction of the EA water is cleaning. Alternatively, for example, thecell can be configured to produce a greater volume of anolyte thancatholyte if the primary function of the EA water is sanitizing. Also,the concentrations of reactive species in each can be varied.

For example, the cell can have a 3:2 ratio of cathode plates to anodeplates for producing a greater volume of catholyte than anolyte. Eachcathode plate is separated from a respective anode plate by a respectiveion exchange membrane. Thus, in this embodiment there are three cathodechambers for two anode chambers. This configuration produces roughly 60%catholyte to 40% anolyte. Other ratios can also be used.

Also, the duty cycle of the applied voltage and/other electricalcharacteristics can be modified to modify the relative amounts ofcatholyte and anolyte produced by the cell.

2.2. Electrolysis Cell with No Ion-Selective Membrane Example

FIG. 3 illustrates an electrolysis cell 80 having no ion-selectivemembrane according to a further example of the disclosure. Cell 80includes a reaction chamber 82, an anode 84 and a cathode 86. Chamber 82can be defined by the walls of cell 80, by the walls of a container orconduit in which electrodes 84 and 86 are placed, or by the electrodesthemselves, for example. Anode 84 and cathode 86 may be made from anysuitable material or a combination of materials, for example stainlesssteel, a conductive polymer, titanium and/or titanium coated with aprecious metal, such as platinum. Anode 84 and cathode 86 are connectedto a conventional electrical power supply, such as batteries 32 shown inFIG. 1. In one embodiment, electrolytic cell 80 includes its owncontainer that defines chamber 82 and is located in the flow path of theliquid to be treated, such as within the flow path of a hand-held spraybottle or mobile floor cleaning apparatus.

During operation, liquid for example is supplied by a source 88 andintroduced into reaction chamber 82 of electrolysis cell 80. In theembodiment shown in FIG. 3, electrolysis cell 80 does not include an ionexchange membrane that separates reaction products at anode 84 fromreaction products at cathode 86. In the example in which tap water isused as the liquid to be treated for use in cleaning, after introducingthe water into chamber 82 and applying a voltage potential between anode84 and cathode 86, water molecules in contact with or near anode 84 areelectrochemically oxidized to oxygen (O₂) and hydrogen ions (H⁺) whilewater molecules in contact or near cathode 86 are electrochemicallyreduced to hydrogen gas (H₂) and hydroxyl ions (OH⁻). Other reactionscan also occur and the particular reactions depend on the components ofthe liquid. The reaction products from both electrodes are able to mixand form an oxygenated fluid 89 (for example) since there is no physicalbarrier, for example, separating the reaction products from each other.Alternatively, for example, anode 84 can be separated from cathode 84 byusing a dielectric barrier such as a non-permeable or other membrane(not shown) disposed between the anode and cathode.

2.3. Dispenser Example

The anolyte and catholyte EA liquid outputs from FIG. 2 or theoxygenated fluid 89 in FIG. 3 can be coupled to a dispenser 74, whichcan include any type of dispenser or dispensers, including for examplean outlet, fitting, spigot, spray head, a cleaning/sanitizing tool orhead, or combination thereof, etc. In the example shown in FIG. 1,dispenser 74 includes spray nozzle 14. There can be a dispenser for eachoutput 70 and 72 in FIG. 2 or a combined dispenser for both outputs.

In one example, the anolyte and catholyte outputs in FIG. 2 are blendedinto a common output stream 76, which is supplied to dispenser 74. Asdescribed in Field et al. U.S. Patent Publication No. 2007/0186368, ithas been found that the anolyte and catholyte can be blended togetherwithin the distribution system of a cleaning apparatus and/or on thesurface or item being cleaned while at least temporarily retainingbeneficial cleaning and/or sanitizing properties. Although the anolyteand catholyte are blended, in this example they are initially not inequilibrium and therefore can temporarily retain their enhanced cleaningand/or sanitizing properties.

For example, in one embodiment, the catholyte EA water and the anolyteEA water maintain their distinct electrochemically activated propertiesfor at least 30 seconds, for example, even though the two liquids areblended together. During this time, the distinct electrochemicallyactivated properties of the two types of liquids do not neutralizeimmediately. This allows the advantageous properties of each liquid inthis example to be utilized during a common cleaning operation. After arelatively short period of time, the blended anolyte and catholyte EAliquid on the surface being cleaned may quickly neutralize substantiallyto the original pH and ORP of the source liquid (e.g., those of normaltap water). In one example, the blended anolyte and catholyte EA liquidneutralize substantially to a pH between pH6 and pH8 and an ORP between±50 mV within a time window of less than 1 minute or other combinationsfrom the time the anolyte and catholyte EA outputs are produced by theelectrolysis cell. Other appropriate pH ranges may result. Thereafter,the recovered liquid can be disposed in any suitable manner.

In other embodiments, the blended anolyte and catholyte EA liquid canmaintain e.g. pHs outside of the range between pH6 and pH8 and ORPsoutside the range of ±50 mV for a time greater than 30 seconds, and/orcan neutralize after a time range that is outside of 1 minute, dependingon an embodiment and the properties of the liquid.

3. Dirt, and Cleaning with Electrolyzed Water Example

The following discussion as with the other example discussions herein isprovided as an example only and not intended to limit the presentdisclosure, operation of examples described herein and/or the scope ofany issued claims appended hereto.

3.1 Example of Basic Concepts

Dirt consists of mixtures of dried-on previously-soluble matter, oilymaterial and/or insoluble particles, for example. Generally dirt has agreater affinity for more dirt than it has for water.

To remove dirt, the affinity between dirt particles and other dirtparticles, and between the dirt particles and the surface being cleaned,should be reduced and the affinity of dirt particles for water should beincreased.

Usually, soaps and detergents are used on oily dirt to form micelles,and polyanions are used to suspend dirt particles. In one exemplaryembodiment of the disclosure, neither of these are present in theelectrolyzed water dispensed from nozzle 14.

However during the electrolysis process, some nanobubbles are created atthe electrode surfaces and then slowly dissipate within the anolyte andcatholyte EA liquids produced by the electrolysis cell, as shown in FIG.4A. Other nanobubbles are created at the dirt surface from thesupersaturated EA water solution that is dispensed from the spraybottle. These nanobubbles can exist for significant periods of time bothin the aqueous solution and at submerged solid/liquid surfaces.

The nanobubbles tend to form and stick to hydrophobic surfaces, such asthose that are found on typical dirt particles, as shown in FIG. 4B.This process is energetically favored as the attachment of the gasbubbles releases water molecules from the high energy water/hydrophobicsurface interface with a favorable negative free energy change.

Also, as the bubbles contact the surface, the bubbles spread out andflatten, which reduces the bubbles' curvatures; giving additionalfavorable free energy release.

Further, the presence of nanobubbles on the surface of dirt particlesincreases the pick-up of the particle by larger micron-plus sized gasbubbles, possibly introduced by mechanical cleaning/wiping action and/orthe prior electrolytic sparging process, as shown in FIG. 4C. Thepresence of surface nanobubbles also reduces the size of the dirtparticle that can be picked up by this action.

Such pick-up helps float away the dirt particles from the surfaces beingcleaned and prevents re-deposition, as shown in FIG. 4D.

A further property of nanobubbles is their vast gas/liquid surface areafor their volume. Water molecules at this interface are held by fewerhydrogen bonds, as recognized by water's high surface tension. Due tothis reduction in hydrogen bonding to other water molecules, theinterface water is more reactive than ‘normal’ water and will hydrogenbond to other molecules more rapidly, showing faster hydration.

Due at least in part to these illustrative (example) properties, thecombined anolyte and catholyte EA liquid in certain embodiments that iscreated and dispensed from the spray bottle shown in FIG. 1 has enhancedcleaning properties as compared to non-electrolyzed water.

3.2 Example Reactions

With respect to the electrolysis cell 50 shown in FIG. 2, watermolecules in contact with anode 60 are electrochemically oxidized tooxygen (O₂) and hydrogen ions (H⁺) in the anode chamber 54 while watermolecules in contact with the cathode 62 are electrochemically reducedto hydrogen gas (H₂) and hydroxyl ions (OH⁻) in the cathode chamber 56.The hydrogen ions in the anode chamber 54 are allowed to pass throughthe cation-exchange membrane 58 into the cathode chamber 56 where thehydrogen ions are reduced to hydrogen gas while the oxygen gas in theanode chamber 54 oxygenates the feed water to form the anolyte 70.Furthermore, since regular tap water typically includes sodium chlorideand/or other chlorides, the anode 60 oxidizes the chlorides present toform chlorine gas. As a result, a substantial amount of chlorine isproduced and the pH of the anolyte composition 70 becomes increasinglyacidic over time.

As noted, water molecules in contact with the cathode 62 areelectrochemically reduced to hydrogen gas and hydroxyl ions (OH⁻) whilecations in the anode chamber 54 pass through the cation-exchangemembrane 58 into the cathode chamber 56 when the voltage potential isapplied. These cations are available to ionically associate with thehydroxyl ions produced at the cathode 62, while hydrogen gas bubblesform in the liquid. A substantial amount of hydroxyl ions accumulatesover time in the cathode chamber 56 and reacts with cations to formbasic hydroxides. In addition, the hydroxides remain confined to thecathode chamber 56 since the cation-exchange membrane does not allow thenegatively charged hydroxyl ions pass through the cation-exchangemembrane. Consequently, a substantial amount of hydroxides is producedin the cathode chamber 56, and the pH of the catholyte composition 72becomes increasingly alkaline over time.

The electrolysis process in the functional generator 50 allowsconcentration of reactive species and the formation of metastable ionsand radicals in the anode chamber 54 and cathode chamber 56.

The electrochemical activation process typically occurs by either e.g.electron withdrawal (at anode 60) or electron introduction (at cathode62), which leads to alteration of physiochemical (including structural,energetic and catalytic) properties of the feed water. It is believedthat the feed water (anolyte or catholyte) gets activated in theimmediate proximity of the electrode surface where the electric fieldintensity can reach a very high level. This area can be referred to asan electric double layer (EDL).

While the electrochemical activation process continues, the waterdipoles generally align with the field, and a proportion of the hydrogenbonds of the water molecules consequentially break. Furthermore,singly-linked hydrogen atoms bind to the metal atoms (e.g., platinumatoms) at cathode electrode 62, and single-linked oxygen atoms bind tothe metal atoms (e.g., platinum atoms) at the anode electrode 60. Thesebound atoms diffuse around in two dimensions on the surfaces of therespective electrodes until they take part in further reactions. Otheratoms and polyatomic groups may also bind similarly to the surfaces ofanode electrode 60 and cathode electrode 62, and may also subsequentlyundergo reactions. Molecules such as oxygen (O₂) and hydrogen (H₂)produced at the surfaces may enter small cavities in the liquid phase ofthe water (e.g., bubbles) as gases and/or may become solvated by theliquid phase of the water. These gas-phase bubbles are thereby dispersedor otherwise suspended throughout the liquid phase of the feed water.

The sizes of the gas-phase bubbles may vary depending on a variety offactors, such as the pressure applied to the feed water, the compositionof the salts and other compounds in the feed water, and the extent ofthe electrochemical activation. Accordingly, the gas-phase bubbles mayhave a variety of different sizes, including, but not limited tomacrobubbles, microbubbles, nanobubbles, and/or mixtures thereof. Inembodiments including macrobubbles, examples of suitable average bubblediameters for the generated bubbles include diameters ranging from about500 micrometers to about one millimeter. In embodiments includingmicrobubbles, examples of suitable average bubble diameters for thegenerated bubbles include diameters ranging from about one micrometer toless than about 500 micrometers. In embodiments including nanobubbles,examples of suitable average bubble diameters for the generated bubblesinclude diameters less than about one micrometer, with particularlysuitable average bubble diameters including diameters less than about500 nanometers, and with even more particularly suitable average bubblediameters including diameters less than about 100 nanometers.

Surface tension at a gas-liquid interface is produced by the attractionbetween the molecules being directed away from the surfaces of anodeelectrode 60 and cathode electrode 62 as the surface molecules are moreattracted to the molecules within the water than they are to moleculesof the gas at the electrode surfaces. In contrast, molecules of the bulkof the water are equally attracted in all directions. Thus, in order toincrease the possible interaction energy, surface tension causes themolecules at the electrode surfaces to enter the bulk of the liquid.

In the embodiments in which gas-phase nanobubbles are generated, the gascontained in the nanobubbles (i.e., bubbles having diameters of lessthan about one micrometer) are also believed to be stable forsubstantial durations in the feed water, despite their small diameters.While not wishing to be bound by theory, it is believed that the surfacetension of the water, at the gas/liquid interface, drops when curvedsurfaces of the gas bubbles approach molecular dimensions. This reducesthe natural tendency of the nanobubbles to dissipate.

Furthermore, nanobubble gas/liquid interface is charged due to thevoltage potential applied across membrane 58. The charge introduces anopposing force to the surface tension, which also slows or prevents thedissipation of the nanobubbles. The presence of like charges at theinterface reduces the apparent surface tension, with charge repulsionacting in the opposite direction to surface minimization due to surfacetension. Any effect may be increased by the presence of additionalcharged materials that favor the gas/liquid interface.

The natural state of the gas/liquid interfaces appears to be negative.Other ions with low surface charge density and/or high polarizability(such as Cl⁻, ClO⁻, HO₂ ⁻, and O₂ ⁻) also favor the gas/liquidinterfaces, as do hydrated electrons. Aqueous radicals also prefer toreside at such interfaces. Thus, it is believed that the nanobubblespresent in the catholyte (i.e., the water flowing through cathodechamber 56) are negatively charged, but those in the anolyte (i.e., thewater flowing through anode chamber 54) will possess little charge (theexcess cations cancelling out the natural negative charge). Accordingly,catholyte nanobubbles are not likely to lose their charge on mixing withthe anolyte.

Additionally, gas molecules may become charged within the nanobubbles(such as O₂ ⁻), due to the excess potential on the cathode, therebyincreasing the overall charge of the nanobubbles. The surface tension atthe gas/liquid interface of charged nanobubbles can be reduced relativeto uncharged nanobubbles, and their sizes stabilized. This can bequalitatively appreciated as surface tension causes surfaces to beminimized, whereas charged surfaces tend to expand to minimizerepulsions between similar charges. Raised temperature at the electrodesurface, due to the excess power loss over that required for theelectrolysis, may also increase nanobubble formation by reducing localgas solubility.

As the repulsion force between like charges increases inversely as thesquare of their distances apart, there is an increasing outwardspressure as a bubble diameter decreases. The effect of the charges is toreduce the effect of the surface tension, and the surface tension tendsto reduce the surface whereas the surface charge tends to expand it.Thus, equilibrium is reached when these opposing forces are equal. Forexample, assuming the surface charge density on the inner surface of agas bubble (radius r) is Φ(e⁻/meter²), the outwards pressure(“P_(out)”), can be found by solving the NavierStokes equations to give:

P _(out)=Φ²/2D∈ ₀  (Equation 1)

where “D” is the relative dielectric constant of the gas bubble (assumedunity), “∈₀” is the permittivity of a vacuum (i.e., 8.854 pF/meter). Theinwards pressure (“P_(in)”) due to the surface tension on the gas is:

P _(in)=2g/rP _(out)  (Equation 2)

where “g” is the surface tension (0.07198 Joules/meter² at 25° C.).Therefore if these pressures are equal, the radius of the gas bubble is:

r=0.28792∈₀/Φ².

Accordingly, for nanobubble diameters of 5 nanometers, 10 nanometers, 20nanometers, 50 nanometers, and 100 nanometers the calculated chargedensity for zero excess internal pressure is 0.20, 0.14, 0.10, 0.06 and0.04 e⁻/nanometer² bubble surface area, respectively, for example. Suchcharge densities are readily achievable with the use of an electrolysiscell (e.g., electrolysis cell 18). The nanobubble radius increases asthe total charge on the bubble increases to the power ⅔. Under thesecircumstances at equilibrium, the effective surface tension of theliquid at the nanobubble surface is zero, and the presence of chargedgas in the bubble increases the size of the stable nanobubble. Furtherreduction in the bubble size would not be indicated as it would causethe reduction of the internal pressure to fall below atmosphericpressure. In various situations within the electrolysis cell (e.g.,electrolysis cell 18), the nanobubbles may divide into even smallerbubbles due to the surface charges. For example, assuming that a bubbleof radius “r” and total charge “q” divides into two bubbles of sharedvolume and charge (radius r½=r/2^(1/3), and charge q_(1/2)=q/2), andignoring the Coulomb interaction between the bubbles, calculation of thechange in energy due to surface tension (ΔE_(ST)) and surface charge(ΔE_(q)) gives:

ΔE _(ST)=+2(4πγr _(1/2) ²)−4πγr ²=4πγr ²(2^(1/3)−1)  (Equation 3)

and

$\begin{matrix}{{\Delta \; E_{q}} = {{{{- 2}( {\frac{1}{2} \times \frac{( {q/2} )^{2}}{4{\pi ɛ}_{0}r_{1/2}}} )} - {\frac{1}{2} \times \frac{q^{2}}{4{\pi ɛ}_{0}r}}} = {\frac{q^{2}}{8{\pi ɛ}_{0}r}( {1 - 2^{{- 2}/3}} )}}} & ( {{Equation}\mspace{14mu} 4} )\end{matrix}$

The bubble is metastable if the overall energy change is negative whichoccurs when ΔE_(ST)+ΔE_(q) is negative, thereby providing:

$\begin{matrix}{{{\frac{q^{2}}{8{\pi ɛ}_{0}r}( {1 - 2^{{- 2}/3}} )} + {4{\pi\gamma}\; {r^{2}( {2^{1/3} - 1} )}}} \leq 0} & ( {{Equation}\mspace{14mu} 5} )\end{matrix}$

which provides the relationship between the radius and the chargedensity (Φ):

$\begin{matrix}{\Phi = {\frac{q}{4\pi \; r^{2}} \geq \sqrt{\frac{2{\gamma ɛ}_{0}}{r}\frac{( {2^{1/3} - 1} )}{( {1 - 2^{{- 2}/3}} )}}}} & ( {{Equation}\mspace{14mu} 6} )\end{matrix}$

Accordingly, for nanobubble diameters of 5 nanometers, 10 nanometers, 20nanometers, 50 nanometers, and 100 nanometers the calculated chargedensity for bubble splitting 0.12, 0.08, 0.06, 0.04 and 0.03e⁻/nanometer² bubble surface area, respectively. For the same surfacecharge density, the bubble diameter is typically about three timeslarger for reducing the apparent surface tension to zero than forsplitting the bubble in two. Thus, the nanobubbles will generally notdivide unless there is a further energy input.

The above-discussed gas-phase nanobubbles are adapted for example toattach to dirt particles, thereby transferring their ionic charges. Thenanobubbles stick to hydrophobic surfaces, which are typically found ontypical dirt particles, which releases water molecules from the highenergy water/hydrophobic surface interface with a favorable negativefree energy change. Additionally, the nanobubbles spread out and flattenon contact with the hydrophobic surface, thereby reducing the curvaturesof the nanobubbles with consequential lowering of the internal pressurecaused by the surface tension. This provides additional favorable freeenergy release. The charged and coated dirt particles are then moreeasily separated one from another due to repulsion between similarcharges, and the dirt particles enter the solution as colloidalparticles.

Furthermore, the presence of nanobubbles on the surface of particlesincreases the pickup of the particle by micron-sized gas-phase bubbles,which may also be generated during the electrochemical activationprocess. The presence of surface nanobubbles also reduces the size ofthe dirt particle that can be picked up by this action. Such pickupassist in the removal of the dirt particles from floor surfaces andprevents re-deposition. Moreover, due to the large gas/liquid surfacearea-to-volume ratios that are attained with gas-phase nanobubbles,water molecules located at this interface are held by fewer hydrogenbonds, as recognized by water's high surface tension. Due to thisreduction in hydrogen bonding to other water molecules, this interfacewater is more reactive than normal water and will hydrogen bond to othermolecules more rapidly, thereby showing faster hydration.

For example, at 100% efficiency a current of one ampere is sufficient toproduce 0.5/96,485.3 moles of hydrogen (H₂) per second, which equates to5.18 micromoles of hydrogen per second, which correspondingly equates to5.18×22.429 microliters of gas-phase hydrogen per second at atemperature of 0° C. and a pressure of one atmosphere. This also equatesto 125 microliters of gas-phase hydrogen per second at a temperature of20° C. and a pressure of one atmosphere. As the partial pressure ofhydrogen in the atmosphere is effectively zero, the equilibriumsolubility of hydrogen in the electrolyzed solution is also effectivelyzero and the hydrogen is held in gas cavities (e.g., macrobubbles,microbubbles, and/or nanobubbles).

Assuming the flow rate of the electrolyzed solution is 0.12 U.S. gallonsper minute, there is 7.571 milliliters of water flowing through theelectrolysis cell each second. Therefore, there are 0.125/7.571 litersof gas-phase hydrogen within the bubbles contained in each liter ofelectrolyzed solution at a temperature of 20° C. and a pressure of oneatmosphere. This equates to 0.0165 liters of gas-phase hydrogen perliter of solution less any of gas-phase hydrogen that escapes from theliquid surface and any that dissolves to supersaturate the solution.

The volume of a 10 nanometer-diameter nanobubble is 5.24×10⁻²² liters,which, on binding to a hydrophobic surface covers about 1.25×10⁻¹⁶square meters. Thus, in each liter of solution there would be a maximumof about 3×10⁻¹⁹ bubbles (at 20° C. and one atmosphere) with combinedsurface covering potential of about 4000 square meters. Assuming asurface layer just one molecule thick, for example, this provides aconcentration of active surface water molecules of over 50 millimoles.While this concentration represents an exemplary maximum amount, even ifthe nanobubbles have greater volume and greater internal pressure, thepotential for surface covering remains large. Furthermore, only a smallpercentage of the dirt particles surfaces need to be covered by thenanobubbles for the nanobubbles to have a cleaning effect.

Accordingly, the gas-phase nanobubbles, generated during theelectrochemical activation process, are beneficial for attaching to dirtparticles so transferring their charge. The resulting charged and coateddirt particles are more readily separated one from another due to therepulsion between their similar charges. They will enter the solution toform a colloidal suspension. Furthermore, the charges at the gas/waterinterfaces oppose the surface tension, thereby reducing its effect andthe consequent contact angles. Also, the nanobubbles coating of the dirtparticles promotes the pickup of larger buoyant gas-phase macrobubblesand microbubbles that are introduced. In addition, the large surfacearea of the nanobubbles provides significant amounts of higher reactivewater, which is capable of the more rapid hydration of suitablemolecules.

4. Tubular Electrode Example

As mentioned above, the electrolysis cell 18 shown in FIG. 1 can haveany suitable shape or configuration, such as those shown in FIGS. 2 and3. The electrodes themselves can have any suitable shape, such asplanar, coaxial plates, cylindrical rods, or a combination thereof.

FIG. 5 illustrates an example of an electrolysis cell 200 having atubular shape according to one illustrative example. For example, cell200 can include the electrolysis cell contained in a hand-held spraybottle that is distributed by, and available from, a licensee of theassignee of this application, ActiveIon Cleaning Solutions, LLC of St.Josephs, Minn. under the name “Activeion™ Pro.”

Electrolysis cell 200 can be used in any of the embodiments disclosedherein, for example. The radial cross-section of cell 200 can have anyshape, such as circular as shown in FIG. 5, or other shapes such ascurvilinear shapes having one or more curved edges and/or rectilinearshapes. Specific examples include ovals, polygons, such as rectangles,etc.

Portions of cell 200 are cut away for illustration purposes. In thisexample, cell 200 is an electrolysis cell having a tubular housing 202,a tubular outer electrode 204, and a tubular inner electrode 206, whichis separated from the outer electrode by a suitable gap, such as 0.040inches. Other gap sizes can also be used, such as but not limited togaps in the range of 0.020 inches to 0.080 inches. Either of the inneror outer electrode can serve as the anode/cathode, depending upon therelative polarities of the applied voltages.

An ion-selective membrane 208 is positioned between the outer and innerelectrodes 204 and 206. In one example, outer electrode 204 and innerelectrode 206 have conductive polymer constructions with apertures.However, one or both electrodes can have a solid construction in anotherexample.

The electrodes 204 and 206 can be made from any suitable material, forexample a conductive polymer, titanium and/or titanium coated with aprecious metal, such as platinum, or any other suitable electrodematerial. In addition, multiple cells 200 can be coupled in series or inparallel with one another, for example.

In a specific example, at least one of the anode or cathode electrodesis formed of a metallic mesh, with regular-sized rectangular openings inthe form of a grid. In one specific example, the mesh is formed of0.023-inch diameter T316 (or, e.g. 304) stainless steel having a gridpattern of 20×20 grid openings per square inch. However, otherdimensions, arrangements and materials can be used in other examples.

An ion-selective membrane 208 is positioned between the outer and innerelectrodes 204 and 206. In one specific example, the ion-selectivemembrane includes a “NAFION” from E.I. du Pont de Nemours and Company,which has been cut to 2.55 inches by 2.55 inches and then wrapped aroundinner tubular electrode 206 and secured at the seam overlap with acontact adhesive, for example, such as a #1357 adhesive from 3M Company.Again, other dimensions and materials can be used in other examples.Other examples of suitable membranes include the other membranesdescribed herein and, for example, those available from MembranesInternational Inc. of Glen Rock, N.J., such as the CMI-7000S cationexchange membrane and the AMI-7001S anion exchange membrane.

In this example, at least a portion of the volume of space within theinterior of tubular electrode 206 is blocked by a solid inner core 209to promote liquid flow along and between electrodes 204 and 206 andion-selective membrane 208, in a direction along the longitudinal axisof housing 202. This liquid flow is conductive and completes anelectrical circuit between the two electrodes. Electrolysis cell 200 canhave any suitable dimensions. In one example, cell 200 can have a lengthof about 4 inches long and an outer diameter of about ¾ inch. The lengthand diameter can be selected to control the treatment time and thequantity of bubbles, e.g., nanobubbles and/or microbubbles, generatedper unit volume of the liquid.

Cell 200 can include a suitable fitting at one or both ends of the cell.Any method of attachment can be used, such as through plasticquick-connect fittings. For example, one fitting can be configured toconnect to the output tube 20 shown in FIG. 1. Another fitting can beconfigured to connect to the inlet filter 16 or an inlet tube, forexample. In another example, one end of cell 200 is left open to drawliquid directly from reservoir 12 in FIG. 1.

In the example shown in FIG. 5, cell 200 produces anolyte EA liquid inthe anode chamber (between one of the electrodes 204 or 206 andion-selective membrane 208) and catholyte EA liquid in the cathodechamber (between the other of the electrodes 204 or 206 andion-selective membrane 208). The anolyte and catholyte EA liquid flowpaths join at the outlet of cell 200 as the anolyte and catholyte EAliquids enter tube 20 (in the example shown in FIG. 1). As a result,spray bottle 10 dispenses a blended anolyte and catholyte EA liquidthrough nozzle 14.

In one example, the diameters of tubes 20 and 22 are kept small so thatonce pump 24 and electrolysis cell 18 (e.g., cell 200 shown in FIG. 5)are energized, tubes 20 and 22 are quickly primed withelectrochemically-activated liquid. Any non-activated liquid containedin the tubes and pump are kept to a small volume. Thus, in theembodiment in which the control electronics 30 activate pump andelectrolysis cell in response to actuation of switch 28, spray bottle 10produces the blended EA liquid at nozzle 14 in an “on demand” fashionand dispenses substantially all of the combined anolyte and catholyte EAliquid (except that retained in tubes 20, 22 and pump 24) from thebottle without an intermediate step of storing the anolyte and catholyteEA liquids. When switch 28 is not actuated, pump 24 is in an “off” stateand electrolysis cell 18 is de-energized. When switch 28 is actuated toa closed state, control electronics 30 switches pump 24 to an “on” stateand energizes electrolysis cell 18. In the “on” state, pump 24 pumpswater from reservoir 12 through cell 18 and out nozzle 14.

Other activation sequences, configurations and arrangements can also beused. For example, control circuit 30 can be configured to energizeelectrolysis cell 18 for a period of time before energizing pump 24 inorder to allow the feed water to become more electrochemically activatedbefore dispensing.

The travel time from cell 18 to nozzle 14 can be made very short. In oneexample, spray bottle 10 dispenses the blended anolyte and catholyteliquid within, e.g., a very small period of time from which the anolyteand catholyte liquids are produced by electrolysis cell 18. For example,the blended liquid can be dispensed within time periods such as within 5seconds, within 3 seconds, and within 1 second of the time at which theanolyte and catholyte liquids are produced.

If desired, further structures of one or more particular non-limitingexamples of the tubular electrolysis cell 200 are shown and described inField U.S. patent application Ser. No. 12/488,360, filed Jun. 19, 2009,which is hereby incorporated by reference in its entirety. Thesestructures can be used in any of the embodiments disclosed herein andmodifications thereof.

5. Additional High-Voltage Electrode Enhancing Santitization Propertiesof Electrolyzed Output Example

While the electrolyzed liquid produced by an electrolysis cell may haveenhanced cleaning properties, it may be desired to further enhance thesanitizing properties of the anolyte, catholyte and/or combinedanolyte/catholyte liquid that is produced by the cell.

For example, depending on the characteristics of the voltage applied tothe electrolysis cell and the properties of the liquid (e.g., tap water)fed to the cell, the chemical properties of the liquid produced by thecell may not be sufficient to produce consistent sanitizing properties.While the electrolysis process produces certain amounts of hydrochlorousacid, which can have sanitizing properties, typical electrolysisprocesses rely on “salt doping” to effect charge transfer through theliquid, and there can be inconsistent “salts” in tap water. This canlead to unpredictable concentrations of hydrochlorous acid andunpredictable sanitizing properties.

It has been found that in one or more of the embodiments of the presentdisclosure that the electrodes in the electrolysis cell generate, e.g.,a small electrical charge in the liquid. It has also been found thatliquid path from the electrolysis cell to the surface or volume beingtreated by the output spray can be electrically conductive, relative toEarth ground, for example. The electrical potential between one or moreof the cell electrodes and Earth ground can enhance sanitization ofmicroorganisms on the surface or in the volume contacted by the liquid.

The electrical potential is applied e.g. through the liquid and/orliquid/gas mixture to the microorganisms and, if the resulting electricfield applied across the cells of the microorganism is of a sufficientmagnitude, the electric field can cause irreversible damage ordestruction to the microorganisms through a mechanism such aselectroporation and/or elecrohydraulic shock, as discussed in moredetail below.

In an illustrative embodiment of the present disclosure, the electricalcharge delivered through the liquid dispensed by the hand-held deviceshown in FIG. 1 can be further enhanced by a separate electricalconductor, lead, or other electrical and/or electromagnetic component,for example, an electrode, e.g., high voltage (in a relative sense)electrode 35, to impart, apply, induce or otherwise cause an electricalpotential in a liquid output spray and/or stream. In the example shownin FIG. 1, electrode 35 is positioned in the liquid path to cause aseparate, greater electrical potential relative to Earth ground, ascompared to the potential generated by electrolysis cell 18, forexample. Also in the example shown in FIG. 1, electrode 35 is positionedalong tube 22. However, electrode 35 can be located at any positionalong the liquid flow path from reservoir 12 to nozzle 14 (or evenexternal to spray bottle 10) or other position as appropriate, e.g., toconduct electrical charge to charge or additionally charge liquiddispensed by the hand-held device.

In one example, electrode 35 is formed by an electrically conductivespike or “barb”, which is inserted through the side wall of tube 22 so aportion of the electrode comes into physical contact with liquid flowingthrough tube 22. In another example, tube 22 is made at least partiallyof an electrically conductive material, such as a metal and/or aconductive polymer. For example, tube 22 can include a section made ofcopper, which is electrically connected to an electrical lead extendingfrom control electronics 30. In an exemplary embodiment, the additionalelectrode 35 is separate from and external to electrolysis cell 18 andhas no corresponding return electrode (e.g., an electrode of oppositepolarity and/or an electrode representing a circuit ground for theelectroporation electrode). It will be appreciated that otherarrangements in other embodiments may be utilized.

The power supply on control electronics 30 can be configured to deliveran AC and/or DC voltage (such as a positive voltage) to lead 35 and thusto the liquid in tube 22. Tube 22 is configured to conduct electricityfrom lead 35 to liquid being delivered through the tube and thus applyan electrical potential and/or additional electrical potential to liquidentering nozzle 14. This additional electrical potential can increasethe electroporation/electrohydraulic shock inflicted on themicroorganisms, for example.

Various voltages and voltage patterns can be used in alternativeembodiments. Earth ground serves to complete the electrical circuitformed by electrode 35, the liquid stream delivered by nozzle 14, andthe surface or volume to which the stream is applied.

The additional voltage (and/or current) can be applied at any locationalong the flow path of bottle 10, from reservoir 12 to the output ofnozzle 14 (or externally to bottle 10) for example. For example, ifnozzle 14 is at least partially conductive, lead 35 can be coupled tonozzle 14. In other examples, lead 35 is electrically coupled to a probetip that is in contact with the liquid at any location along the flowpath. In another example, lead 35 is electrically coupled to the housingof pump 24, which, if conductive, delivers the electrical charge to theliquid passed through the pump. In yet a further example, the lead 35can deliver additional electrical charge to liquid contained withinelectrolysis cell 18. In yet a further example, the electrolysis cell 18is eliminated from bottle 10, wherein liquid sprayed from nozzle 14 isnot electrochemically activated but can still carry an electrical chargeas a result of a conductor such as lead 35 for causingelectroporation/electrohydraulic shock.

5.1 Example High—Voltage, Electroporation Electrode

FIG. 6 is an exploded view of a high-voltage electroporation electrode35 according to an illustrative embodiment of the disclosure. Electrode35 includes an adapter 240, a washer 242, a terminal 244 and a nut 246.Adapter 240 has two opposing ends with male connectors (e.g., barbs) forconnecting between two sections of tube 22 (shown in FIG. 1), forexample. Adapter 240 has an internal lumen for passing liquid from oneend to the other, along the liquid flow path of the apparatus. Adapter240 can be formed of any suitable material, such as anelectrically-conductive material, such as copper, brass, and/or silver.In one particular embodiment, at least a portion of adapter 240 isformed of or coated with silver. For example, adapter 240 can be formedof brass, wherein at least a portion of the surface in contact with theliquid is coated with silver. For example, the internal and externaldiameter surfaces are coated with silver.

Nut 246 threads onto one end of adapter 240, thereby holding terminal244 and washer 244 in tight electrical contact with the adapter. Anelectrical lead (not shown) can be attached to terminal 244 forelectrically connecting the terminal with the control electronics 30(shown in FIG. 1). Since adapter 240 is electrically conductive, thepotential applied to adapter 240, through terminal 244, is applied tothe liquid flowing through the adapter, relative to the surface beingsprayed.

In another embodiment, electrode 35 is formed by an electricallyconductive spike, which extends through a sidewall of tube 22 such thatthe spike makes electrical contact with liquid flowing through the tube.Other configurations can also be used.

In yet another embodiment, the electrode can be formed by anelectrically conductive nozzle. For example, nozzle 14 in FIG. 1 ornozzle 508 in FIG. 10A can be formed of an at least partially conductivematerial, such as but not limited to, silver-coated brass.

The silver plating may also enhance the sanitization action. Silver mayprovide good electrical conductivity with the liquid flowing along theflow path. It is also possible that, when an electrical potential isapplied to electrode 35 and a current flows from electrode 35 to thesurface through the liquid output spray, silver ions can migrate fromthe electrode into the liquid flow. Silver ions are known to have atoxic effect on some bacteria, viruses, algae and fungi. Therefore, useof a silver electrode can further enhance the sanitization properties ofthe dispensed liquid and/or liquid/gas mixture.

5.2 Electroporation Mechanism Example

The following discussion is provided as an example only and not intendedto limit the present disclosure, operation of examples described hereinand/or the scope of any issued claims appended hereto.

FIG. 7A is a diagram illustrating the spray output 250 from spray nozzle14, wherein individual droplets may take different paths, e.g., “a” and“b” from the nozzle to the surface 252 being treated. Surface 252 may ormay not have an electrical conduction path to ground 254, such as Earthground.

FIG. 7B is a diagram illustrating an example of the electroporationmechanism achieved by spraying surface 252 (in FIG. 7A) with outputspray 250 from spray bottle 10 shown in FIG. 1. The output spray 250dispensed on surface 35 has been found to form a conducting suspensionmedium. FIG. 7B illustrates the resulting electric field “E” applied toa cell membrane 256 of a microorganism that is suspended from surface252 by the dispensed liquid from output spray 250. The output spray 250and the liquid dispensed on surface 252 together form a conductive pathfrom electrode 35 to surface 252, for example. The addition of anapplied alternating potential from electrode 35 to the electrolyticwater spray appears to endow the output spray 250 with significantlyenhanced sanitizing action. This phenomenon has been associated withirreversible electroporation. In one particular embodiment, thealternating potential appears to be particularly effective at 600 V, 28kHz with a variable effect for different organisms. However, othervoltage and frequencies can be used in other embodiments.

Electroporation followed by cell death is known to be achievable with atransmembrane potential of at least 0.5 V (where a membrane thickness istypically ˜3 nm, for example). Depending on the configuration, suchpotentials may require a pulse of about 10 kV/cm or more. Lowerpotentials may be effective, for example in the presence of cell toxinsor with the availability of additional mechanisms for preventingnormally reversibly-formed pores from resealing. It should be noted thatalthough electroporation is commonly used as a ‘reversible’ tool atlower potentials, it is recognized that, even under these conditions,often only a small percentage of cells recover.

The formation of holes in the cell membranes is generally insufficientin itself to cause cell death, as it is known that cells can survive forrelatively long periods with large amounts of membrane missing.

Cell death comes because of disruption to the metabolic state of thecells, which can be caused by electrophoretic and electroosmotic(capillary electrophoretic) movement of materials into and out of thecells. Diffusion by itself is generally too slow. To achieveelectrophoresis and electroosmosis, sufficient power must be dissipatedwithin the surface, as shown in the diagram of FIG. 7C.

Different microorganisms have different total surface charges and chargedistributions and therefore will react differently to each other interms of cell death. They will also behave differently in theoscillating potential field and will have different resonant frequenciesfor maximum absorption (and hence maximum movement relative to theaqueous solution, causing the maximum chaos to their metabolism).Movement in and out depends primarily on potential gradients. Increasedeffects occur when the system is in resonance.

When considering the potential gradient delivered to the cell and thepower dissipated to the sprayed surface, in one particular example, thespray device delivers a fine spray that may be partially a true aerosol(˜1μ droplets), but mostly a mist with droplet sizes much greater than10μ. The droplet sizes and velocity profiles can vary between differentembodiments.

The velocity of the liquid exiting the nozzle is simply calculated fromthe rate of liquid sprayed divided by the area of the exit orifice.However the subsequent decrease in droplet speed depends on the dropletsize (mass to surface area ratio). The terminal velocity of 10μ and 50μdroplets are only about 10⁻³ m/s and 10⁻¹ m/s respectively.

Sprayed water droplets descend at different rates, and the timedifferences will be significant when related to the rapidly alternatingpotential (e.g., 28 kHz). For example, in FIG. 7A, pathway (b) will belonger than pathway (a), for example by about 1 cm. The descent velocity(dependent on the drop size, flow rate and nozzle diameter) willdetermine the difference in time between the drops landing but this islikely to be several to many times the potential cycling time of 36 μs.

If the potential is determined by the time of descent, then significantpotential gradients will exist within the two dimensional surface withgreater field gradients towards the periphery of the sprayed field. Adroplet just 1 cm out from the center still travels an additional about0.03 cm and, even if travelling at 10 m/s, this is equivalent to onecycle of the potential. These potential gradients might exist if thedrops are not in effectively continuous contact with the sprayerelectrode. If all the spray has the same potential on impinging thesurface in spite of the different routes taken (and consequent times ofdescent) of the droplets, then the potential gradients are not withinthe surface as such but between the surface and ‘earth’ and these maynot be sufficient to cause electroporosity if the surface is not‘earthed’.

Cells with open pores are much more prone to the effects of cell toxinsin the aqueous solution as they have no barrier to their entry. Thepotential cell toxins co-delivered with the alternating potential areperoxide, chlorine oxides, and other redox agents such as superoxide,ozone and singlet oxygen, and heavy metal ions such as cupric ionsand/or silver ions.

Charged nanobubbles will move in the electric fields and will be capableof picking up materials from the surface. As they are surface-active,they may additionally interfere with pore resealing and preferentiallydeliver their cytotoxic surface active molecules to the pore sites, asshown in FIG. 7C, for example.

In view of the above, the electrolyzed water produced by spray bottle10, shown in FIG. 1, for example, acts as a cleaning agent due toproduction of tiny electrically-charged bubbles. These attach themselvesto dirt particles/microorganisms so transferring their charge. Thecharged and coated particles separate one from another due to therepulsion between their similar charges and enter the solution as asuspension. Coating of the dirt by tiny bubbles promotes their pick-upby larger buoyant bubbles that are introduced during cleaning, thusaiding the cleaning process. Simultaneously, microorganisms can beelectroporated and killed or otherwise eliminated by the electricpotential generated by the additional electrode 35, e.g. reducing thenumber of microorganisms on a surface.

Thus, to enhance sanitization ability properties, electroporation can beused for example to accomplish a more consistent and effectivedestruction of microbial action by discharging (in a relative sense) ahigh-voltage to a ground (such as Earth ground) through e.g. an aqueousfluid.

It has also been found that the combination of theelectrochemically-activated liquid produced by the electrolysis cell andthe electric field applied by the electroporation electrode has asynergistic effect. It is believed that as the charged nanobubblesproduced in the electrochemically-activated liquid move in the electricfields, they pick up microorganisms and separate them from the surface.By separating the microorganisms from the surface, such that they aresuspended in the liquid on the surface, the electric field producedalong the surface by the electroporation electrode is applied moreeasily across the microorganism cells. Whereas, if the microorganism isin contact with the surface, the electric field is more easilydischarged into the surface ground and may be less effective in creatingirreversible electroporation of the organisms cells. With the cellsuspended, the applied alternating field oscillates back and forthcausing damage to the cells.

In alternative embodiments, microorganism suspension can be accomplishedthrough mechanisms other than electrochemically-activated liquidsproduced by electrolysis cells. For example, the microorganisms can besuspended by using a detergent and/or mechanical action or combination.Particular examples of other suspension mechanisms include, for example,any mechanism that alters the ORP of the dispensed liquid (producingdispensed liquid having a positive ORP, a negative ORP or a combinationof both). For example, it has been found that regular tap water may bealtered to have a negative ORP (such as but not limited to −50millivolts to −600 millivolts) which has enhanced cleaning effects.These enhanced cleaning effects can serve to suspend microorganismsabove the surface within the dispensed liquid, for example. Althoughnegative (and/or positive) ORP can be achieved through an electrolysiscell as described herein, it can also be achieved by other mechanismssuch as by use of surfactants (and/or detergents carrying surfactants),and/or by passing the liquid to be dispensed through a filter or othermechanism containing a material, such as zeolites, that alters the ORPof the liquid.

As describe in more detail herein, zeolites, depending on the type, canimpart a negative ORP (and/or a positive ORP) on liquids such as regulartap water by ion exchange. Thus, in one or more of the embodimentsdisclosed herein, the electrolysis cell is replaced for example by azeolite filter, or a zeolite filter is used in combination with anelectrolysis cell. Such a filter can be positioned for example anywherealong the liquid flow and/or within the source liquid container. Othermaterials or mechanisms suitable for ion exchange, such as a resin orother matrices, may be utilized in other embodiments depending on theirability to impart an altered ORP.

The electroporation electrode may also be used (such as in the variousembodiments disclosed herein) in combination with other wet cleaningtechnologies, such as a chemical-based system that use a chemical withinthe dispensed liquid for inactivating microorganisms, with or withoutuse of an electrolysis cell. These chemical based wet cleaningtechnologies might provide longer residence times and thus greatersanitizing effect on some surfaces, such as porous surfaces, forexample.

5.3 Electroporation by Hand-Held Spray Bottle Example

In the example shown in FIG. 8, an aspect of the disclosure relates to aprocess for deactivating or destroying microorganisms, by applying apotential or electrochemical pressure to microorganisms, in a chargedmedium such as an atomized spray generated by an electrolysis cellcarried by a hand-held spray apparatus 300. However, spray bottle 300can be replaced with any other apparatus or system having anelectrolysis cell and a high-voltage electroporation electrode asdescribed herein.

As shown in FIG. 8, the spray nozzle of the hand-held spray bottle 300dispenses the electrochemically-activated liquid as a charged outputspray 302, which forms an electrically-coupled conduit of spray. As theoutput spray 302 contacts a surface 304, the electrical conduit of spray302 becomes electrically coupled to the surface, thus completing anelectrically conductive path from the cell electrodes and thehigh-voltage electroporation electrode to the surface. This path allowselectrical charge to be delivered to microorganisms present on thesurface.

Further, it has been found that as the surface becomes wet with theliquid carried by the output spray, the electrical charge conductsthroughout and along the wetted surface, as long as there exists aconductive path of liquid between the output spray and various areas onthe surface that are remote from direct contact by the output spray. Ithas been found that an electrical charge can be measured at an arearemote from direct contact by the output spray if the surface has acontinuous path of liquid between the area of direct contact an theremote area at which the measurement is made.

For example, FIG. 9 illustrates a plan view of partially wetted surface304. As spray 302 contacts surface 304, the liquid carried by spray 302forms a conductive path 306, which carries electrical charge from theoutput spray to remote area 308 that is not in direct contact with theoutput spray. This conductive path can serve to increase the length oftime various areas of the surface are treated by the charge as theoutput spray is advanced along the surface.

In one aspect of the disclosure, spray bottle 300 (or other liquiddelivery apparatus) is configured and operated to deliver an electricalcharge through the output liquid in a manner that results in a deliveredcharge magnitude that exceeds a limit of intracellular and extracellularelectrostatic capacity possessed by one or more microorganisms on thesurface being treated. In one example, the apparatus is configured andoperated to achieve a transmembrane potential of at least 0.5 Volts oncells of one or more of the microorganisms on the surface that are incontact with the liquid dispensed from the apparatus.

6. Particular Spray Bottle Example 6.1 Bottle Configuration Example

FIG. 10A illustrates a specific example of a commercial embodiment ofthe spray bottle shown schematically in FIG. 1. The particular bottleconfigurations and constructions shown in the drawings are provided asnon-limiting examples only.

If desired, further structures of one or more particular non-limitingexamples of spray bottle 500 are shown and described in Field U.S.patent application Ser. No. 12/488,368, filed Jun. 19, 2009, which ishereby incorporated by reference in its entirety. These structures canbe used in any of the embodiments disclosed herein and modificationsthereof.

A commercial embodiment is presently available in a hand-held spraybottle form, which is distributed by, and available from, ActiveIonCleaning Solutions, LLC of St. Josephs, Minn. under the name “Activeion™Pro.” The embodiment in the example shown in FIGS. 10A-10C is similar tothe foregoing spray bottle with a modification regarding addition of anelectroporation electrode and related control circuitry, etc.

In FIG. 10A, bottle 500 includes a housing 501 forming a base 502, aneck 504, and a barrel or head 506. The tip of barrel 506 includes anozzle 508 and a drip/splash guard 509. In one example, nozzle 508 isformed of brass. Drip/splash guard 509 also serves as a convenient hookfor hanging bottle 500 on a utility cart, for example. Housing 501 has aclamshell-type construction with substantially symmetrical left andright hand sides attached together, such as by screws. Base 502 houses acontainer 510, which serves as a reservoir for liquid to be treated andthen dispensed through nozzle 508. Container 510 has a neck and threadedinlet (with a screw cap) 512 that extends through base 502 to allowcontainer 510 to be filled with a liquid. Inlet 512 is threaded toreceive a cap seal.

In this example, the entire housing or a portion of the housing is atleast translucent. Similarly, container 510 is formed of a material thatis at least translucent. For example, container 510 can be fabricated asa blow mold of a clear polyester material. As explained in more detailbelow, housing 501 also contains a circuit board carrying a plurality ofLED indicator lights 594, 596. In this example, there are four red LEDs594 and four green LEDs 596 (also shown in phantom), arranged in pairsin each corner of the bottle. The lights are positioned beneath the baseof container 510 to transmit light through a base wall of container 510and into any liquid contained in the container. The liquid diffuses atleast a portion of the light, giving an appearance of the liquid beingilluminated. The color of the light and/or other illuminationcharacteristics such as on/off modulation, intensity, etc. that arecontrolled by the control electronics are observable from an exterior ofthe bottle to give the user an indication of the functional status ofthe bottle.

For example, the liquid can be illuminated with green LEDs to indicatethat the electrolysis cell and/or pump are functioning properly. Thus,the user can be assured that the treated liquid dispensed from nozzle508 has enhanced cleaning and/or sanitizing properties as compared tothe source liquid contained in container 510. Also, illumination of thesource liquid in container 510, although not yet treated, gives animpression that the liquid is “special” and has enhanced properties.

Similarly, if the electrolysis cell and/or pump are not functioningproperly, the control electronics illuminates the red LEDs, giving thesource liquid a red appearance. This gives the user an impression thatthere is a problem and that the dispensed liquid may not have enhancedcleaning and/or sanitizing properties.

FIG. 10B illustrates various components installed in the left-hand side501A of housing 501. Container 510 is installed in compartment 531,circuit board 540 is installed in compartment 532, batteries 542 areinstalled in compartment 533, and pump/cell assembly 544 is installed incompartment 534. The various tubes that connect container 510, pump/cellassembly and nozzle 508 are not shown in FIG. 10B.

The back end of the barrel (or head) 506 of bottle 501 includes anelectrical power jack 523 for connecting to the cord of a batterycharger (not shown). In the example in which bottle 500 carriesrechargeable batteries, these batteries can be recharged through jack523.

FIG. 10C illustrates a fragmentary, close-up view of pump/cell assembly544 installed in the barrel 506 of housing half 501A. Pump/cell assembly544 includes a pump 550 and an electrolysis cell 552 mounted within abracket 554. Electrolysis cell 552 has an inlet 556 that is fluidicallycoupled to a tube (not shown) extending from the outlet of container 510and an outlet 557 that is fluidically coupled through another tube (alsonot shown) to an inlet 555 of pump 550. Pump 550 has an outlet that isfluidically coupled to the inlet 558 of nozzle 508. In one example,electrolysis cell 552 corresponds to the tubular electrolysis cell 200discussed with reference to FIG. 5. However, any suitable electrolysiscell in this and other embodiments disclosed herein, such as thosedisclosed in Field et al. U.S. Publication No. 2007/0186368 A1,including but not limited to the electrolysis cells (e.g., functionalgenerators) disclosed in FIGS. 8A, 8B and 9. O-ring 560 provides a sealabout the nozzle 508 for housing 501. Also, pump 550 can be locatedupstream or downstream of cell 552.

As described above with reference to FIG. 6, in this example, the highvoltage electroporation electrode 35 is fluidically coupled between theoutlet 557 of cell 552 and the inlet 558 of nozzle 508. The electrodeadapter 240 (shown in FIG. 6) is spliced within a tube connecting outlet557 and inlet 558 to provide an electrical connection to the fluidflowing to nozzle 508. However, the electrode 35 can be located at otherlocations along the fluid flow paths of bottle 500.

Bottle 500 further includes a trigger 570, which actuates a momentarypush-button on/off switch 572. Trigger 570 actuates about pivot whendepressed by a user. A spring (not visible in FIG. 10C) biases trigger570 in a normally released state and thus switch 572 in an off state.Switch 572 has electrical leads for connecting to the controlelectronics on circuit board 540, shown in FIG. 10A.

When trigger 570 is depressed, switch 572 actuates to the “on” state,thereby providing electrical power to the control electronics, whichenergizes pump 550 and electrolysis cell 552. When energized, pump 550draws liquid from container 510 and pumps the liquid throughelectrolysis cell 552 and Electroporation electrode adapter 240 (FIG.6), which deliver a combined anolyte and catholyte EA liquid to nozzle508. When pump 550 and/or electrolysis cell 552 are functioningproperly, the control electronics also illuminate the green LEDsinstalled on the circuit board or another location in or on bottle 500.

In an exemplary embodiment, nozzle 508 maintains a fluid stream duringuse that is sufficient to conduct an electric field applied by theelectroporation electrode 35 to the surface or volume of space beingtreated, through the dispensed liquid. With some nozzles, it has beenfound that the nozzle may cause cavitation of the liquid stream that maydisrupt electrical conductivity along the output stream, thuspotentially reducing the electric field applied to the surface beingtreated. Using an electrically conductive nozzle (such as brass, anothermetal, and/or conductive plastic) may help to maintain an electricalconductive path along the relevant or desired liquid path, e.g., fromthe electroporation electrode 35, through the nozzle, to the outputspray that is delivered to the surface, even if some cavitation of theliquid occurs within the nozzle. An illustrative example of a suitablenozzle is a #TT276-1/8M-2 hydraulic atomizing nozzle from SprayingSystems Co., P.O. Box 7900 Wheaton, Ill. Also, this nozzle is used at apressure of 25-40 psi, for example. Other types of nozzles and pressureranges can be used in other examples.

When using a conductive nozzle, such as a brass nozzle, it may also bebeneficial to insulate the outer surface of the nozzle, e.g., with adielectric, such as by using a plastic cap over the nozzle, which has anaperture for the spray output. The plastic cap may limit an electricaldischarge if the nozzle comes in contact with a conductive surface or aperson's skin, for example.

6.2 Control Circuits Example 6.2.1 Driving Voltage for Electrolysis CellExample

FIG. 11 is a waveform diagram illustrating the voltage pattern appliedto the anode and cathode of electrolysis cell 552 (in the bottle shownin FIGS. 10A-10C) according to an exemplary aspect of the presentdisclosure. A substantially constant, relatively positive voltage isapplied to the anode, while a substantially constant, relativelynegative voltage is applied to the cathode. However, periodically eachvoltage is briefly pulsed to a relatively opposite polarity to repelscale deposits. In some examples, there is a desire to limit scaledeposits from building on the electrode surfaces. In this example, arelatively positive voltage is applied to the anode and a relativelynegative voltage is applied to the cathode from times t0-t1, t2-t3,t4-t5 and t6-t7. During times t1-t2, t3-t4, t5-t6 and t7-t8, the voltageapplied to each electrode is reversed. The reversed voltage level canhave the same magnitude as the non-reversed voltage level or can have adifferent magnitude if desired.

The frequency of each brief polarity switch can be selected as desired.As the frequency of reversal increases, the amount of scaling decreases.However, the electrodes may loose small amounts of platinum (in the caseof platinum coated electrodes) with each reversal. As the frequency ofreversals decreases, scaling may increase. In one example, the timeperiod between reversals, as shown by arrow 300, is in the range ofabout 1 second to about 600 seconds. Other periods outside this rangecan also be used. In this example, the time period of normal polarity303, such as between times t2 and t3, is at least 900 milliseconds.

The time period at which the voltages are reversed can also be selectedas desired. In one example, the reversal time period, represented byarrow 302, is in the range of about 50 milliseconds to about 100milliseconds. Other periods outside this range can also be used.

With these ranges, for example, each anode chamber produces asubstantially constant anolyte EA liquid output, and each cathodechamber produces a substantially constant catholyte EA output withoutrequiring valving.

In prior art electrolysis systems, complicated and expensive valving isused to maintain constant anolyte and catholyte through respectiveoutlets while still allowing the polarity to be reversed to minimizescaling.

If the number of anode electrodes is different than the number ofcathode electrodes, e.g., a ratio of 3:2, or if the surface area of theanode electrode is different than the surface area of the cathodeelectrode, then the applied voltage pattern can be used in theabove-manner to produce a greater amount of either anolyte or catholytein the produced liquid. With a tubular electrolysis cell 552 (such ascell 200 shown in FIG. 5), outer cylindrical electrode 204 has a greaterdiameter and therefore a greater surface area than inner cylindricalelectrode 206. To emphasize enhanced cleaning properties, the controlcircuit can be configured, for example, to drives cell 200 so that, fora majority of period of the driving voltage pattern, outer electrode 204(or the greater number of electrodes in embodiments having unequalnumbers of anodes and cathodes) serves as the cathode and innerelectrode 206 (or the lesser number of electrodes in embodiments havingunequal numbers of anodes and cathodes) serves as the anode. Since thecathode has a larger surface area (or number of electrodes) than theanode, cell 200 will e.g. generate more catholyte than anolyte per unitof time through the combined outlet of the cell.

If sanitizing is to be emphasized, then outer electrode 204 (or thegreater number of electrodes) can be driven to the relatively positivepolarity (to produce more anolyte) and the inner electrode (or thelesser number of electrodes) can be driven to the relatively negativepolarity (to produce less catholyte).

Referring to FIG. 11, in this example, the control circuit applies arelatively positive voltage to the anode (electrode 206) and arelatively negative voltage to the cathode (electrode 204) from timest0-t1, t2-t3, t4-t5 and t6-t7. During times t1-t2, t3-t4, t5-t6 andt7-t8, the voltages applied to each electrode is briefly reversed.

It has been found that such frequent, brief polarity reversals forde-scaling the electrodes may have a tendency also to shed materialsoften used for plating the electrodes, such as platinum, from theelectrode surface. Thus in one embodiment, electrodes 204 and 206comprise unplated electrodes, such as metallic electrodes or conductiveplastic electrodes. For example, the electrodes can be unplated metallicmesh electrodes.

In one exemplary embodiment, the spray bottle (or other apparatus) canfurther include a switch that can be used to selectively invert thewaveform shown in FIG. 11 (or any other waveform applied to theelectrolysis cell). For example, the switch can be set in one positionto generate more anolyte than catholyte and in another position togenerate more catholyte than anolyte. The control circuit monitors theswitch position and adjusts the voltage applied to the electrolysis cellaccording to the switch position.

However, the electrodes of the electrolysis cell can be driven with avariety of different voltage and current patterns, depending on theparticular application of the cell.

In another example, the electrodes are driven at one polarity for aspecified period of time (e.g., about 5 seconds) and then driven at thereverse polarity for approximately the same period of time. Since theanolyte and cathotlyte EA liquids are blended at the outlet of the cell,this process produces essentially one part anolyte EA liquid to one partcatholyte EA liquid.

In another example, the cell electrodes are driven with a pulsed DCvoltage waveform, wherein the polarity applied to the electrodes is notreversed. The “on/off” time periods and applied voltage levels can beset as desired.

6.2.2 Control Circuit for Electrolysis Cell Example

The waveform applied to the electrolysis cell is controlled by controlcircuit 30, shown in FIG. 1, which resides, for example, on circuitboard 540 shown in FIG. 10B. Control circuit 30 can include any suitablecontrol circuit and can be implemented in hardware, software, or acombination of both, for example.

Control circuit 30 includes a printed circuit board containingelectronic devices for powering and controlling the operation of pump 24and electrolysis cell 18. In one example, control circuit 30 includes apower supply having an output that is coupled to pump 24 andelectrolysis cell 18 and which controls the power delivered to the twodevices. Control circuit 30 also includes an H-bridge, for example, thatis capable of selectively reversing the polarity of the voltage appliedto electrolysis cell 18 as a function of a control signal generated bythe control circuit. For example, control circuit 30 can be configuredto alternate polarity in a predetermined pattern, such as every 5seconds with a 50% duty cycle. In another example, described above,control circuit 30 is configured to apply a voltage to the cell withprimarily a first polarity and periodically reverse the polarity foronly very brief periods of time.

In the context of a hand-held spray bottle, it is inconvenient to carrylarge batteries. Therefore, the available power to the pump and cell issomewhat limited. In one example, the driving voltage for the cell is inthe range of about 18 Volts to about 28 Volts. But since typical flowrates through the spray bottle and electrolysis cell are fairly low,only relatively small currents are necessary to effectively activate theliquid passing through the cell. With low flow rates, the residence timewithin the cell is relatively large. The longer the liquid resides inthe cell while the cell is energized, the greater the electrochemicalactivation (within practical limits). This allows the spray bottle, forexample, to employ smaller capacity batteries and a DC-to-DC converter,which steps the voltage up to the desired output voltage at a lowcurrent.

In one particular example in which the spray bottle carries four AAbatteries, the batteries may have an output voltage in a range of about3 Volts to about 9 Volts, or for example. For example, each AA batterymay have, for example, a nominal output voltage of 1.5 Volts at about500 milliampere-hours to about 3 ampere-hours. If the batteries areconnected in series, then the nominal output voltage would be about 6Vwith a capacity of about 500 milliampere-hours to about 3 ampere-hours.This voltage can be stepped up to the range of 18 Volts to 28 Volts, orin a range of 18 Volts to 38 Volts, for example, through the DC-to-DCconverter. Thus, the desired electrode voltage can be achieved at asufficient current.

In another particular example, the spray bottle carries ten nickel-metalhydride batteries, each having a nominal output voltage of about 1.2Volts. The batteries are connected in series, so the nominal outputvoltage is about 10 Volts to about 13.8 Volts with a capacity of about1800 milliampere-hours, for example. This voltage is stepped up/down toa range of 8 Volts to at least 28 Volts or to a range of about 8 Voltsto about 38 Volts, for example, through the DC-to-DC converter. Thus,the desired electrode voltage can be achieved at a sufficient current.It will be appreciated that as the sizes of batteries decrease, evensmaller battery sizes, numbers, combinations, or capacities thereof orof other related electrical devices such as converters, etc. may beutilized in alternate embodiments.

The ability to produce a large voltage and a suitable current throughthe cell can be beneficial for applications in which regular tap wateris fed through the cell to be converted into a liquid having enhancedcleaning and/or sanitizing properties. Regular tap water has arelatively low electrical conductivity between the electrodes of thecell.

Examples of suitable DC-to-DC converters include the Series A/SM surfacemount converter from PICO Electronics, Inc. of Pelham, N.Y., U.S.A. andthe NCP3064 1.5A Step-Up/Down/Inverting Switching regulator from ONSemiconductor of Phoenix, Ariz., U.S.A, connected in a boostapplication.

In one example, the control circuit controls the DC-to-DC converterbased on a sensed current drawn from the electrolysis cell so that theDC-to-DC converter outputs a voltage that is controlled to achieve acurrent draw through the cell that is within a predetermined currentrange. For example, the target current draw is about 400 milliamperes inone specific example. In another example, the target current is 350milliamperes. Other currents and ranges can be used in alternativeembodiments. The desired current draw may depend on the geometry of theelectrolysis cell, the properties of the liquid being treated and thedesired properties of the resulting electrochemical reaction.

A block diagram illustrating a particular example of the control circuit30 is shown in FIG. 12. Although the control circuit shown in FIG. 12 isconfigured to control various components of a spray bottle such as thatshown in FIGS. 10A-10C, the control circuit can be used as is ormodified as desired to control similar elements on any other apparatusaccording to alternative embodiments of the present disclosure.

The main components of control circuit 30 include a microcontroller1000, a DC-to-DC converter 1004, and an output driver circuit 1006.

Power to the various components is supplied by a battery pack 542carried by the bottle, as shown in FIG. 10B, for example. In a specificexample, battery pack 542 includes ten nickel-metal hydride batteries,each having a nominal output voltage of about 1.2 Volts. The batteriesare connected in series, so the nominal output voltage is about 10V to12.5V with a capacity of about 1800 milliampere-hours. Hand trigger570,572 (shown in FIGS. 10A-10C, for example) selectively applies the12-volt output voltage from battery pack 542 to voltage regulator 1003and to DC-to-DC converter 1004. Any suitable voltage regulator can beused, such as an LM7805 regulator from Fairchild SemiconductorCorporation. In a particular example, voltage regulator 1003 provides a5 Volt output voltage for powering the various electrical componentswithin the control circuit.

DC-to-DC converter 1004 generates an output voltage to be applied acrossthe electrodes of electrolysis cell 552. The converter is controlled bymicrocontroller 1000 to step the drive voltage up or down in order toachieve a desired current draw through the electrolysis cell. In aparticular example, converter 1004 steps the voltage up or down betweena range of 8 Volts to 28 Volts (or greater) to achieve a current drawthrough electrolysis cell 552 of about 400 milliamps, as pump 550 pumpswater from container 510, through cell 552 and out nozzle 508 (FIGS.10A-10C). The required voltage depends in part on the conductivity ofthe water between the cell's electrodes.

In a particular example, DC-to-DC converter 1004 includes a Series A/SMsurface mount converter from PICO Electronics, Inc. of Pelham, N.Y.,U.S.A. In another example, converter 1004 includes an NCP3064 1.5AStep-Up/Down/Inverting Switching regulator from ON Semiconductor ofPhoenix, Ariz., U.S.A, connected in a boost application. Other circuitsand/or arrangements can be used in alternative embodiments.

Output driver circuit 1006 selectively reverses the polarity of thedriving voltage applied to electrolysis cell 552 as a function of acontrol signal generated by microcontroller 1000. For example,microcontroller 1000 can be configured to alternate polarity in apredetermined pattern, such that shown and/or described with referenceto FIG. 11. Output driver 1006 can also provide an output voltage topump 550. Alternatively, for example, pump 550 can receive its outputvoltage directly from the output of trigger switch 570, 572.

In a particular example, output driver circuit 1006 includes a DRV 8800full bridge motor driver circuit available from Texas InstrumentsCorporation of Dallas, Tex., U.S.A. Other circuits and/or arrangementscan be used in alternative embodiments. The driver circuit 1006 has anH-switch inverter that drives the output voltage to electrolysis cell552 according to the voltage pattern controlled by the microcontroller.The H-switch also has a current sense output that can be used by themicrocontroller to sense the current drawn by cell 552. Sense resistorR_(SENSE) develops a voltage that is representative of the sensedcurrent and is applied as a feedback voltage to microcontroller 1000.Microcontroller 1000 monitors the feedback voltage and controlsconverter 1004 to output a suitable drive voltage to maintain a desiredcurrent draw.

Microcontroller 1000 also monitors the feedback voltage to verify thatelectrolysis cell 552 and/or pump 550 is operating properly. Asdiscussed above, microcontroller 1000 can operate LEDs 594 and 596 as afunction of the current levels sensed by output driver circuit 1006. Forexample, microcontroller 1000 can turn off (or alternatively, turn on)one or both of the sets of LEDs 594 and 596 as a function of whether thecurrent level sensed is above or below a threshold level or within arange.

Output driver circuit 1006 can also deliver a drive voltage to pump 550under the control of microcontroller 1000, which turns the pump on andoff upon actuation of user trigger switch 570, 572. For example, outputdriver circuit 1006 can selectively apply the 12-volt battery voltageand/or the return voltage to pump 550 through a switch, such as a powerMOSFET. In one particular example, the return voltage is selectivelygated with an IRF7603pbF power MOSFET available from InternationalRectifier of El Segundo, Calif.

Microcontroller 1000 can include any suitable controller, processor,and/or circuitry. In a particular embodiment, it includes anMC9S08SH4CTG-ND Microcontroller available from Digi-Key Corporation ofThief River Falls, Minn., U.S.A.

In the example shown in FIG. 12, the illumination control portion of thecircuit includes output resistors R1 and R2 and a first, “red” LEDcontrol leg formed by pull-up resistor R3, red LED diodes D1-D4, andpull-down transistor Q1. Microcontroller 1000 has a first controloutput, which selectively turns on and off red LEDs D1-D4 by turning onand off transistor Q1. The illumination control portion of the circuitfurther a second, “green” LED control leg formed by pull-up resistor R4,green LED diodes D5-D8, and pull-down transistor Q2. Microcontroller1000 has a second control output, which selectively turns on and offgreen LEDs D5-D8 by turning on and off transistor Q2.

The control circuit further includes a control header 1002, whichprovides an input for programming microcontroller 1000.

In one particular example, the elements 1000, 1002, 1003, 1004, 1006,R1-R4, D1-D8 and Q1-Q2 reside on circuit board 540, shown in FIG. 10B.

In addition, the control circuit shown in FIG. 12 can include a chargingcircuit (not shown) for charging the batteries within battery pack 542with energy received through the power jack 523 shown in FIGS. 10B and10C.

One or more of the control functions described herein can be implementedin hardware, software, firmware, etc., or a combination thereof. Suchsoftware, firmware, etc. is stored on a computer-readable medium, suchas a memory device. Any computer-readable memory device can be used,such as a disc drive, a solid state drive, CD-ROM, DVD, flash memory,RAM, ROM, a set of registers on an integrated circuit, etc.

6.2.3 Driving Voltage for Electroporation Electrode Example

The electroporation electrode 35 (such as adapter 240 in FIG. 6) can bedriven with any suitable driving voltage pattern to achieve the desiredmicroorganism de-activation level. The electrical characteristics of thedriving voltage pattern will be based on the design of the apparatus andthe method of application of the liquid to the microorganism.

In one example of a spray bottle disclosed herein, the driving voltageapplied to the electrode has a frequency in the range of 25 kilohertz to800 kilohertz and a voltage of 50 Volts to 1000 Volts root-mean-square(rms). However, the applied current can be very low, such as but notlimited to the order of 0.15 milliamps. The voltage pattern can be a DCpattern, and AC pattern or a combination of both. The voltage waveformcan be any suitable type such as square, sinusoidal, triangular,sawtooth, and/or arbitrary (from arbitrary pattern generator). In oneexample, the waveform sequentially changes between various waveforms.The positive (or alternatively negative) side of the voltage potentialis applied to the electrode, and the potential of the surface (or volumeof space) being treated serves as the circuit ground (such as Earthground), for example. In addition, the waveforms and voltage levels mayaffect different microorganisms differently. So these parameters can bemodified to enhance killing of particular microorganisms or can bevaried during application to treat effectively a variety of differentorganisms.

Examples of suitable voltages applied to the electroporation electrodeinclude but are not limited to AC voltages in a range of 50 Vrms to 1000Vrms, 500 Vrms to 700 Vrms, or 550 Vrms to 650 Vrms. One particularembodiment applies an voltage of about 600 Vrms to the electroporationelectrode.

Examples of frequencies for the voltage that is applied to theelectroporation electrode include but are not limited to thosefrequencies within a range of 20 KHz to 100 KHz, 25 KHz to 50 KHz, 30KHz to 60 KHz, or about 28 Khz to about 40 KHz. One particularembodiment applies the voltage at about 30 KHz to the electroporationelectrode.

FIG. 13A is a waveform diagram illustrating the voltage pattern appliedto electroporation electrode 35 in one particular example. In thisexample, the shape of the waveform is a combination of a sine wave and asquare wave. However, the waveform can have other shapes, such as a sinewave, a square wave, or other waveform. The applied voltage has an ACvoltage of 600 Volts rms (about 1000V to 1200 Volts peak-to-peak) whenliquid is flowing through adapter 240 of the electrode and has afrequency of about 30 KHz. In this example, the frequency remainssubstantially constant as the apparatus (e.g., spray bottle) dispenseselectrochemically-activated liquid to the surface being treated. Inanother example, the frequency is maintained in a range of about 41KHz-46 KHz.

In another example, the frequency varies over a predefined range whilethe apparatus (e.g., spray bottle) dispenses electrochemically-activatedliquid to the surface being treated. For example, the control circuitthat drives electroporation electrode 35 can sweep the frequency withina range between a lower frequency limit and an upper frequency limit,such as between 20 KHz and 100 KHz, between 25 KHz and 50 KHz, andbetween 30 KHz and 60 KHz.

FIG. 13B is a waveform diagram illustrating the frequency with respectto time of the voltage applied to electroporation electrode 35 inanother particular example. In this example, the frequency ramps, with atriangular waveform, from the low frequency limit to the high frequencylimit and then back down to the low frequency limit over a period ofabout 1 second, for example. In another example, the control circuitramps the frequency from the from the low frequency limit to the highfrequency limit (and/or from the high frequency limit to the lowfrequency limit) over a time period of 0.1 second to 10 seconds. Otherramp frequency ranges can also be used, and the respective ramp-up andramp-down periods can be the same or different from one another. Sincedifferent microorganisms might be susceptible to irreversibleelectroporation at different frequencies, the killing effect of theapplied voltage is swept between different frequencies to potentiallyincrease effectiveness on different microorganisms. For example,sweeping the frequency might be effective in applying the potential atdifferent resonant frequencies of different microorganisms.

In the example shown in FIG. 13C, the frequency is swept between 30 KHzand 60 KHz with a sawtooth waveform. Other waveforms can also be used.

6.2.4 Control Circuit for Electroporation Electrode Example

FIG. 14 is a block diagram illustrating an example of a control circuit1100 for providing a voltage potential to electroporation electrode 35.Circuit 1100 includes a voltage input connector 1102, a voltageregultator 1104, a tri-color LED 1106, microcontroller 1108, switchingpower controller 1110, H-bridge circuits 1112 and 1114, transformer1116, voltage divider 1118, sense resistor 1120 and output connector1122.

Input connector 1102 receives the 12-Volt battery supply voltage fromthe main circuit board, shown in FIG. 12 for example, and supplies thevoltage to voltage regulator 1104, switching power controller 1110 andH-bridge circuits 1112 and 1114. In a particular example, voltageregulator 1104 provides a 5 Volt output voltage for powering the variouselectrical components within the control circuit 1100, such asmicrocontroller 1108, LED 1106 and Switching power controller 1110. Anysuitable voltage regulator can be used, such as an LM7805 regulator fromFairchild Semiconductor Corporation.

In this embodiment microcontroller 1108 has three main functions;providing a clock signal (SYNC) and an enable signal (ENABLE) toswitching power regulator 1110, monitoring for fault conditions, andproviding a user an indication of a fault condition through LED 1106. Inone example, microcontroller 1108 comprises an ATtiny24 QPNMicrocontroller available from ATMEL Corporation. Other controllers canbe used in alternative embodiments.

The clock signal SYNC provides a reference frequency for switching powercontroller 1110. Enable signal ENABLE, when active, enables (or turnson) switching power controller 1110. Normally, microcontroller 1108 setsENABLE to an active state and monitors the FAULT signal for a faultcondition. When no fault condition is present, microcontroller 1108selectively turns on one or more colors of the tri-color LED 1106. Inone example, LED 1106 is a tri-color red, green, blue LED. However,multiple, separate LEDs can be used in alternative embodiments. Further,other types of indicators can be used in addition or in replace of LED1106, such as any visual, audible or tactile indicator. In the presentexample, microcontroller 1108 illuminates a blue LED by pulling therespective cathode low when no fault condition is present.

When controller 1110 indicates a fault condition by activating thesignal FAULT, microcontroller 1108, selectively pulses the ENABLE signalto an inactive state and then returns it to the active state to resetswitching power controller 1110. If the fault condition clears,microcontroller continues to illuminate the blue LED. If the faultcondition remains active, then microcontroller turns off the blue LEDand illuminates a red LED. The green LED is not used, but could be usedin alternative embodiments. Other user indication patterns can be usedin alternative embodiments.

In one example, switching power controller 1110 includes a TPS68000 CCFLPhase Shift Full Bridge CCFL Controller available from TexasInstruments. However, other types of controllers can be used inalternative embodiments.

Based on the SYNC signal, switching power controller 1110 provides gatecontrol signals to the gates of switching transistors within theH-bridge circuits 1112 and 1114. In one example, H-bridge circuits 1112and 1114 each include an FDC6561AN Dual N-Channel Logic Level MOSFET(although other circuits can be used), which are connected together toform an H-bridge inverter that drives the primary side of transformer1116 with the desired voltage pattern, such as that shown in FIG. 13.Transformer 1116 has a 1:100 turn ratio, which steps the drive voltagefrom about 10V-13V peak-to-peak up to about 1000V to 1300 V peak-to-peak(about 600 V rms), for example, when liquid is being dispensed from theapparatus. The output drive voltage is applied to the electroporationelectrode 35 through output connector 1122.

Voltage divider 1118 comprises a pair of capacitors that are connectedin series between the primary side of the transformer and ground todevelop a voltage that is feed back to switching power controller 1110and represents the voltage developed on the secondary side of thetransformer. This voltage level is used to detect an over-voltagecondition. If the feedback voltage exceeds a given threshold, switchingpower controller 1110 will activate fault signal FAULT.

Sense resistor 1120 is connected between the primary side of thetransformer and ground to develop a further feedback voltage that isfeed back to switching power controller 1110 and represents the currentflowing through the secondary side of the transformer. This voltagelevel is used to detect an over-current condition. If the feedbackvoltage exceeds a given threshold, switching power controller 1110 willactivate fault signal FAULT, indicating a fault in the transformer.

In addition, the source of the bottom transistor in one leg of theH-bridge is fed back to switching power controller 1110, as shown byarrow 1124. This feedback line can be monitored to measure the currentin the primary side of the transformer, which can represent the currentdelivered to the load through electroporation electrode 35. Again, thiscurrent can be compared against a high and/or a low threshold level. Theresult of the comparison can be used to set the state of fault signalFAULT.

7. Other Exemplary Apparatus for Delivering Electrical Charge Through anOutput Liquid.

The features and methods described herein, such as those of theelectrolysis cell and/or the electroporation electrode, can be used in avariety of different apparatus, for example, including on a spraybottle, a mobile surface cleaner, and/or a free-standing or wall-mountplatform.

For example, they can be implemented onboard (or off-board) a mobilesurface cleaner, such as a mobile hard floor surface cleaner, a mobilesoft floor surface cleaner or a mobile surface cleaner that is adaptedto clean both hard and soft floors or other surfaces, an all-surfacecleaner, truck-mounted sprayer, high-pressure bathroom sprayer, toiletsand urinals, for example.

7.1 Mobile Surface Cleaner Example

FIG. 15 illustrates an example of a mobile hard and/or soft floorsurface cleaner 1200 disclosed in Field et al. U.S. Publication No.2007/0186368 A1, which can be modified to implement one or more of theabove-described features and/or methods. FIG. 15 is a perspective viewof cleaner 1200 having its lid in an open position.

In this example, cleaner 1200 is a walk-behind cleaner used to cleanhard floor surfaces, such as concrete, tile, vinyl, terrazzo, etc. inother examples, cleaner 1200 can be configured as a ride-on, attachable,or towed-behind cleaner for performing a cleaning and/or sanitizingoperation as described herein. In a further example, cleaner 1200 can beadapted to clean soft floors, such as carpet, or both hard and softfloors in further embodiments. Cleaner 1200 may include electricalmotors powered through an on-board power source, such as batteries, orthrough an electrical cord. Alternatively, for example, an internalcombustion engine system could be used either alone, or in combinationwith, the electric motors.

Cleaner 1200 generally includes a base 1202 and a lid 1204, which isattached along one side of the base 1202 by hinges (not shown) so thatlid 1204 can be pivoted up to provide access to the interior of base1202. Base 1202 includes a tank 1206 for containing a liquid or aprimary cleaning and/or sanitizing liquid component (such as regular tapwater) to be treated and applied to the floor surface duringcleaning/sanitizing operations. Alternatively, for example, the liquidcan be treated onboard or offboard cleaner 1200 prior to containment intank 1206. In addition, cleaner 1200 includes an electrolysis cell 1208,which treats the liquid prior to the liquid being applied to the floorbeing cleaned. Electrolysis cell 1208 can include, for example, one ormore electrolysis cells (in parallel or in series with one another)similar to the one shown and discussed above with reference to FIG. 5 orfor example, one or more of the electrolysis cells disclosed in Field etal. U.S. Publication No. 2007/0186368 A1, including but not limited tothe electrolysis cells (e.g., functional generators) disclosed in FIGS.8A and 8B. For example, the electrolysis cell shown in FIGS. 8A and 8Bcan include an unmodified or modified Emco Tech “JP102” cell foundwithin the JP2000 ALKABLUE LX, which is commercially available from EmcoTech Co., LTD, of Yeupdong, Goyang-City, Kyungki-Do, South Korea. Thisparticular cell has a DC range of 27 Volts, a pH range of about 10 toabout 5.0, a cell size of 62 mm by 109 mm by 0.5 mm, and five electrodeplates. In an example modified version, the JP102 cell is modified toremove a valve mechanism that is supplied with the JP102 cell (andselectively routes the anolyte and catholyte to separate, respectiveoutlets) such that produced anolyte and catholyte mix together to formblended anolyte and catholyte EA water, for example, which is directedto an outlet of the cell. Other types of electrolysis cells can also beused, which can have various different specifications.

The treated liquid can be applied to the floor directly and/or through acleaning head 1210, for example. The treated liquid that is applied tothe floor can include an anolyte EA liquid stream, a catholyte EA liquidstream, both and anolyte and catholyteEA liquid streams and/or acombined anolyte and catholyte EA liquid stream, as described above withreference to FIG. 2, for example. The cell 1208 can include an ionselective membrane or be configured without an ion selective membrane.

In one example, to enhance the electroporation/electrohydraulic shockproperties of the output liquid, the liquid flow path is applieddirectly to the floor to avoid disruption of the electrical conductionpath between the electrolysis cell and the floor that is formed by theliquid flow path. The liquid can be applied in any form, such as astream, an aerosolizing mist, and/or a spray.

In one example, (with or without electrolysis cell 1208), cleaner 1200is further modified to include a further electrical conductor or lead,for example an electroporation electrode (such as electrode 35 shown inFIGS. 1 and 6), at any location along, or in appropriate relation to,the liquid flow path. This electrode can become electrically connectedto the floor being treated via liquid flowing through the flow path. Inone example, the electrode is located at a position very near the pointat which the liquid is output from the cleaner, such as along adispensing tube 1212 near cleaning head 1210. Alternatively or inaddition, the electrode can be located near a spray nozzle thatdispenses an output spray or stream ahead of cleaning head 1210, onto orthrough the cleaning head, or behind the cleaning head, for example,with respect to a direction of travel of cleaner 1200. The electrode canhave any suitable construction, shape or material, for example.

If desired, further structures of one or more particular non-limitingexamples of the mobile cleaner 1200 are shown and described in moredetail in Field et al U.S. Publication No. 2007/018368, which isincorporated by reference in its entirety above. These structures can beused in any of the embodiments disclosed herein and modificationsthereof. The details of at least one particular example are described inFIGS. 10A-10C and 11, for example, of U.S. Publication No. 2007/018368.

Field et al. U.S. Publication No. 2007/0186368 A1 also discloses otherstructures on which the various structural elements and processesdisclosed herein can be utilized either separately or together. Forexample, Field et al. disclose a wall mount platform for generatinganolyte and catholyte EA liquid. Any of these apparatus can beconfigured according to disclosure herein in order to provide anelectric field to a surface being treated while the surface is beingcleaned and/or sanitized.

In another embodiment, the mobile cleaner 1200 does not include anelectrolysis cell but e.g. in addition or instead includes a detergentdispenser, which dispenses detergent with source liquid to the surfacebeing cleaned. The detergent in combination with a mechanical action ofthe cleaning head can suspend microorganisms in liquid on the surface sothat they may be more easily electroporated by an electric field appliedby an electroporation electrode as disclosed herein.

7.2 All Surface Cleaner Example

FIG. 16 is a perspective view of an example of an all surface cleaningassembly 1300, which is described in more detail in U.S. Pat. No.6,425,958, which is incorporated herein by reference in its entirety.The cleaning assembly 1300 is modified to include a liquid distributionpath with one or more electrolysis cells and/or one or moreelectroporation electrodes described herein such as but not limited tothose shown or described with reference to FIGS. 1-3 and 5-6, forexample, or any of the other embodiments disclosed herein.

Cleaning assembly 1300 can be constructed to deliver and optionallyrecover one or more of the following liquids, for example, to and fromthe floor being cleaned: anolyte EA water, catholyte EA water, blendedanolyte and catholyte EA water, or other electrically-charged liquids.For example, liquid other than or in addition to water can be used.

Cleaning assembly 1300 can be used to clean hard surfaces in restroomsor any other room having at least one hard surface, for example.Cleaning assembly 1300 includes the cleaning device and the accessoriesused with the cleaning device for cleaning the surfaces, as described inU.S. Pat. No. 6,425,958. Cleaning assembly 1300 includes a housing 1301,a handle 1302, wheels 1303, a drain hose 1304 and various accessories.The accessories can include a floor brush 1305 having a telescoping andextending handle 1306, a first piece 1308A and a second piece 1308B of atwo piece double bend wand, a spray gun 1310 and various additionalaccessories not shown in FIG. 16, including a vacuum hose, a blowerhose, a sprayer hose, a blower hose nozzle, a squeegee floor toolattachment, a gulper tool, and a tank fill hose (which can be coupled toports on assembly 1300). The assembly has a housing that carries a tankor removable liquid container and a recovery tank or removable recoveryliquid container. The cleaning assembly 1300 is used to clean surfacesby spraying the cleaning liquid through a sprayer hose and onto thesurfaces. The blower hose is then used to blow dry the surfaces and toblow the fluid on the surfaces in a predetermined direction. The vacuumhose is used to suction the fluid off of the surfaces and into therecovery tank within cleaning device 1300, thereby cleaning thesurfaces. The vacuum hose, blower hose, sprayer hose and otheraccessories used with cleaning assembly 1300 can be carried with thecleaning device 1300 for easy transportation. Spray gun 1310 is attachedto a liquid outlet 1312 of cleaner 1300 through a hose 1314.

An electroporation electrode can be located at any location along, or inappropriate relation to, the liquid flow path, which for example canbecome electrically connected to the surface being treated by via liquidflowing through the flow path. For example, the electrode can be locatedat the spray head of spray gun 1310, along the spray hose and/or at anysuitable location on the assembly, such as near the outlet 1303. Thecleaning device also carries the control circuits for the electrolysiscell and the electroporation electrode.

In another example, a wall-mounted platform supports an electrolysiscell and/or electroporation electrode along the liquid flow path from aninlet of the platform to an outlet of the platform. In this embodiment,a hose or other liquid dispenser, for example, would carry the liquid tothe point of application to the surface being treated.

10. Flat Mop Example

FIG. 17 is a diagram illustrating an example of a flat mop embodiment,which includes at least one electrolysis cell and/or at least oneelectrical conductor, lead and/or electromagnetic component to impart,induce or otherwise cause an electrical potential in the liquid outputspray, for example an electroporation electrode, such as those describedherein in the present disclosure.

In this example, flat mop 1400 includes a stiff backing 1402, which canbe fitted with a cleaning pad 1404, such as a micro-fiber pad or cloth.A handle 1405 extends from the backing 1402 and carries a reservoir 1406and a compartment 1408. Reservoir 1406 is adapted to hold a sourceliquid, such as regular tap water, and can be filled through a fill port1410. Reservoir 1406 supplies the source liquid to compartment 1408,which can include, for example, a pump, at least one electrolysis celland/or at least one electroporation electrode, and respective and/orcombined control electronics.

On one particular example, compartment 1408 includes the component partsof the hand-held spray device shown and described with reference toFIGS. 5, 6, 10A-10C and 11-14 (or any of the other examples orembodiments described herein, for example). Compartment 1408 includes aspray nozzle 1412, similar to spray nozzle 508 in FIGS. 10A-10C. Anelectroporation electrode is coupled at any suitable location in theliquid flow path from reservoir 1406 to nozzle 1412, such as at alocation close to the nozzle. Nozzle sprays or otherwise dispenses anoutput spray or stream 1414 toward the surface being cleaned and/orsanitized, wherein the dispensed liquid can be electrochemicallyactivated as described herein, for example. In addition, or in thealternative, the electroporation electrode applied an electric fieldthrough the output spray 1414 to the surface, which for example, issufficient to cause irreversible electroporation of microorganisms onthe surface.

Handle 1405 includes a switch 1416, which is operable by a user similarto trigger 570 in FIGS. 10A-10C, to selectively energize the pump,electrolysis cell, and electroporation electrode. For example, switch1416 can include a momentary or non-momentary push button or trigger.

11. Stationary (or Portable) Device Example

FIG. 18 is a diagram illustrating an example device 1500, which can bestationary or movable relative to a surface 1502. In one example, device1500 includes the component parts of the hand-held spray device shownand described with reference to FIGS. 5, 6, 10A-10C and 11-14 (or any ofthe other examples or embodiments described herein, for example), whichcan include, for example, a pump, at least one electrolysis cell and/orat least one electroporation electrode, and respective and/or combinedcontrol electronics. Device 1500 includes an outlet 1502, which spraysor otherwise dispenses an output spray or stream 1504 to the surface1506 and/or item being cleaned and/or sanitized. Surface 1506 can bestationary and/or movable relative to device 1500. The arrangement canbe adapted to clean and/or sanitize the surface 1506 itself and/or oneor more items carried by the surface. For example, the surface caninclude a table surface or a conveyor carrying product. The dispensedliquid 1504 can be electrochemically activated as described herein. Inaddition, or in the alternative, an electroporation electrode can becoupled at any suitable location in the liquid flow path, such as at alocation close to the outlet 1502, wherein the electroporation electrodeapplies an electric field through the dispensed liquid 1504 to thesurface or item, which for example, is sufficient to cause irreversibleelectroporation of microorganisms on the surface or item.

12. Further System Example

FIG. 19 is a diagram, which illustrates a system 1600 according to anexample embodiment of the disclosure, which can be incorporated into anyof the embodiments disclosed herein, for example. System 1600 includespower supply (such as a battery) 1602, control electronics 1604,electrolysis cell 1606, pump 1608, current sensors 1610 and 1612, anelectroporation electrode 1614, switch 1618 and trigger 1620. Forsimplicity, the liquid inputs and outputs of electrolysis cell 1604 arenot shown in FIG. 19. All elements of system 1600 can be powered by thesame power supply 1602 or by two or more separate power supplies, forexample.

Control electronics 1604 are coupled to control the operating state ofelectrolysis cell 1606, pump 1608 and electrode based on the presentoperating mode of system 1600 and user control inputs, such as trigger1620. In this example, switch 1618 is coupled in series between powersupply 1602 and control electronics 1604 and serves to couple anddecouple power supply 1602 to and from power inputs of controlelectronics 1604 depending on the state of trigger 1620. In oneembodiment, switch 1618 includes a momentary, normally-open switch thatcloses when trigger 1620 is depressed and opens when trigger 1620 isreleased.

In an alternative example, switch 1618 is configured as an on/off toggleswitch, for example, that is actuated separately from trigger 1620.Trigger 1620 actuates a second switch that is coupled to an enable inputof control electronics 1604. The same switch 1618 can be used to controlpower to the various devices 1606, 1608 and 1614 or separate switchescan be used. Also, the same or separate power supplies and/or sourcescan be used to power the various devices 1606, 1608 and 1614. Inaddition, the same or separate control circuits can be used to controlthe voltages applies the electrolysis cell 1606, pump 1608 and electrode1614. Other configurations can also be used.

In one example, when trigger 1620 is depressed, control electronics 1604is enabled and generates appropriate voltage outputs for drivingelectrolysis cell 1606, pump 1608 and electrode 1614. For example,control electronics 1604 can produce a first voltage pattern for drivingthe electrolysis cell 1606, a second voltage pattern for driving pump1608, and a third voltage pattern for electrode 1614, such as thosepatterns described herein. When trigger 1620 is released, controlelectronics is powered off and/or otherwise disabled from producing theoutput voltages to cell 1606 and pump 1608.

Current sensors 1610 and 1612 are coupled in electrical series withelectrolysis cell 1606 and pump 1608, respectively, and each provide asignal to control electronics 1604 that is representative of therespective electrical current drawn through cell 1606 or pump 1606. Forexample, these signals can be analog or digital signals. Controlelectronics 1604 compares the sensor outputs to predetermined thresholdcurrent levels or ranges and then operates indicators 1614 and 1616 as afunction of one or both of the comparisons. The threshold current levelsor ranges can be selected to represent predetermined power consumptionlevels, for example. The bottle can also be provided with a visuallyperceptible indicator(s), such as one or more LEDs 1622 and 1624, whichcan illuminate in different colors or illumination patterns to indicatedifferent operating states, for example.

In addition, a switch can be placed in series with electrode 1614 (or asa control input to control electronics 404) to selectively disableelectrode 1614 when enhanced sanitization properties are not needed.Disabling electrode 1614 may lengthen the battery life or charge stateof power source 1602, when a small power supply is used.

13. Test Results—Examples

The present disclosure is more particularly described in the followingexamples that are intended as illustrations only, since numerousmodifications and variations within the scope of the present disclosurewill be apparent to those skilled in the art. Unless otherwise noted,all parts, percentages, and ratios reported in the following examplesare on a weight basis, and component weight percents are based on theentire weight of the membrane, excluding any reinforcement matrix used.All reagents used in the examples were obtained, or are available, fromthe chemical suppliers described below, from general chemical supplierssuch as Sigma-Aldrich Company, Saint Louis, Mo., or may be synthesizedby conventional techniques.

13.1 Example 1: Electric Field Measurements

Electric field measurements were conducted on a spray bottle of Example1, which was based on the embodiments shown and described with referenceto FIGS. 5, 6, 10A-10C and 11-14 above. Five measurements were made ateach linear position from the spray nozzle of Example 1 along the sprayaxis. The average results are plotted in FIG. 20. For comparisonpurposes with the water spray results, a length of rubber hose wasattached to the outlet of the spray bottle and the electrical potentialrelative to ground was measured across a 1 MegaOhm load at the end ofthis water stream. The rubber hose was then shortened and themeasurement repeated until the measurement position was near the sprayernozzle. The water stream forms a true electrical conductive path, andfour measurements were taken at each position.

FIG. 20A plots the potential field (Vpeak-peak) as a function ofdistance from the nozzle (inches). FIG. 20B plots the electric field(Volts peak-peak/cm) linearly as a function of distance from the nozzle(inches), which was calculated from the potential field data usingtwo-point numerical differentiation.

As seen in FIGS. 20A and 20B, the magnitude of the electric field and/orpotential delivered to the surface (and thus a microorganism on orsuspended near the surface) depends in part on the distance between thenozzle tip and the surface. The maximum distance for applying a givenelectric field to a surface will vary based on the electrical parametersof the control circuit, the applied voltage and waveforms, etc. and themagnitude of the desired field to be delivered. In one example of thehand-held spray device shown in FIGS. 5-6 and 10-14, a suitable electricfield was delivered at distances from zero to about eight inches. Inother embodiments, a suitable field was delivered at distances of up tosix inches. Again, these distances can vary from one embodiment to thenext and depending on the type of microorganisms being treated. Suitableranges for the distance between the nozzle and the surface for effectingirreversible electroporation of one or more microorganisms on thesurface include, for example, zero to ten inches, zero to eight inches,zero to six inches, zero to 4 inches and zero to 3 inches. In oneexample, a desired distance is 3-4 inches.

Experimental test results also showed a correlation between thenozzle/surface distance and the spray duration for removing and killingmicroorganisms (e.g., bacteria). In general, the closer the nozzle is tothe receiving surface, a shorter the spray duration may be. For example,a spray duration of two seconds at a distance ranging from 3-4 inchesbetween nozzles and the receiving surfaces achieved substantial killresults against Escherichia coli (E. coli) and Bacillus bacteria. Thisis believed to be due to the greater magnitudes of the electric fieldsand/or potentials that were delivered to the surfaces due to the reducednozzle/surface distances.

13.2 Example 2: Antimicrobial Efficacy

The efficacy of a spray bottle of Example 2 in reducing bacteriaconcentrations was also measured. The experiment was performed pursuantto American Society for Testing and Materials (ASTM) E1153-03,established by ASTM International, West Conshohocken, Pa., which is atest method used to evaluate antimicrobial efficacy of sanitizers oninanimate, non-porous, non-food contact surfaces. Separate samples oftreated carriers contained Staphylococcus aureus (ATCC #6538) and E.coli (ATCC #11229).

The spray bottle of Example 2 was the same as the spray bottle ofExample 1, described above, where the spray bottle of Example 2 was alsofilled with tap water for the experiment. The test method was modifiedby spraying the treated carriers for four seconds with the spray bottleof Example 2 at a distance of ranging from three to four inches from thetreated carriers, and with an ambient temperature of 20° C. One-third ofthe treated carriers were then wiped after being sprayed with a wipe tosimulate a wiping action, where the wipe used was commercially availableunder the trade designation “WYPALL” All Purpose Wipes fromKimberly-Clark Corporation, Neenah, Wis. Another third of the treatedcarriers remained unwiped to measure the efficacy of the spray itself.The final third of the treated carriers were oversprayed, which involvedspraying a fine mist in the air, which then deposited onto the treatedcarriers. Each test was performed in duplicate, referred to as Run 1 andRun 2.

Tables 1 and 2 illustrate the antimicrobial efficacy of the spray bottleof Example 2 respectively against Staphylococcus aureus and E. coli.“CFU” refers to “colony forming unit”, and the “average percentreduction” and the “average log₁₀ reduction” were calculated based onthe averages of Runs 1 and 2.

TABLE 1 Staphylococcus Aureus Log₁₀ Average CFU/ Average % Log₁₀ ExampleTest Carrier Reduction Reduction Example 2 Carrier - Run 1<1.6 >99.999% >5.2 Example 2 Carrier - Run 2 <1.6 Example 2 Wipe - Run 1<1.6 >99.999% >5.2 Example 2 Wipe - Run 2 <1.6 Example 2 Overspray - Run1 <1.6 >99.999% >5.2 Example 2 Overspray - Run 2 <1.6

TABLE 2 E. coli Log₁₀ Average CFU/ Average % Log₁₀ Example Test CarrierReduction Reduction Example 2 Carrier - Run 1 <1.6 >99.999% >5.2 Example2 Carrier - Run 2 <1.6 Example 2 Wipe - Run 1 <1.6 >99.999% >5.2 Example2 Wipe - Run 2 <1.6 Example 2 Overspray - Run 1 <1.6 >99.999% >5.2Example 2 Overspray - Run 2 <1.6

The results shown in Tables 1 and 2 illustrate the efficacy of the spraybottle of the present disclosure for removing and killing a variety ofmicroorganisms. The sprayed carrier (without wiping), the wiped carrier,and the oversprayed carrier each provided an antimicrobial efficacygreater than 99.999% for each of the tested microorganisms.

13.3 Examples 3 and 4: Antimicrobial Efficacy

The efficacy of spray bottles of Examples 3 and 4 in reducing bacteriaconcentrations was also measured. The experiment was performed in thesame manner as discussed above for Example 2, where separate samples oftreated carriers contained E. coli O157:H7 (ATCC #35150), Salmonellaenterica (ATCC #10708), Pseudomonas aeruginosa (ATCC #15442),Vancomycin-resistant Enterococcus (VRE) (ATCC #51575), andMethicillin-resistant Staphylococcus aureus (MRSA) (ATCC #33592).

The spray bottles of Examples 3 and 4 were the same as the spray bottleof Example 1, described above, where the spray bottles of Examples 3 and4 were also filled with tap water for the experiment. The test methodwas modified by spraying the treated carriers for six seconds with thespray bottles of Examples 3 and 4 at a distance of ranging from three tofour inches from the treated carriers, and with an ambient temperatureof 21° C. One-third of the treated carriers were then wiped after beingsprayed with a wipe to simulate a wiping action, where the wipe used wascommercially available under the trade designation “WYPALL” All PurposeWipes from Kimberly-Clark Corporation, Neenah, Wis. Another third of thetreated carriers remained unwiped to measure the efficacy of the sprayitself. The final third of the treated carriers were oversprayed, whichinvolved spraying a fine mist in the air, which then deposited onto thetreated carriers. Each test was performed in duplicate, referred to asRun 1 and Run 2.

Tables 3-7 illustrate the antimicrobial efficacy of the spray bottles ofExamples 3 and 4 against the tested microorganisms, where the “averagepercent reduction” and the “average log₁₀ reduction” were calculatedbased on the averages of Runs 1 and 2.

TABLE 3 E. coli O157:H7 Log₁₀ Average CFU/ Average % Log₁₀ Example TestCarrier Reduction Reduction Example 3 Carrier - Run 1<0.0 >99.9999%  >6.7 Example 3 Carrier - Run 2 <0.0 Example 3 Wipe - Run1 <1.6 >99.999% >5.1 Example 3 Wipe - Run 2 <1.6 Example 3 Overspray -Run 1 <1.7 >99.999% >5.0 Example 3 Overspray - Run 2 <1.7 Example 4Carrier - Run 1 <0.0 >99.9999%  >6.7 Example 4 Carrier - Run 2 <0.0Example 4 Wipe - Run 1 <1.6 >99.999% >5.1 Example 4 Wipe - Run 2 <1.6Example 4 Overspray - Run 1 <1.7 >99.999% >5.0 Example 4 Overspray - Run2 <1.7

TABLE 4 Salmonella Enterica Log₁₀ Average CFU/ Average % Log₁₀ ExampleTest Carrier Reduction Reduction Example 3 Carrier - Run 10.8 >99.9999%  >6.2 Example 3 Carrier - Run 2 <0.0 Example 3 Wipe - Run1 <1.6 >99.99% >4.9 Example 3 Wipe - Run 2 <1.6 Example 3 Overspray -Run 1 <1.7 >99.99% >4.9 Example 3 Overspray - Run 2 <1.7 Example 4Carrier - Run 1 <0.0 >99.9999%  >6.6 Example 4 Carrier - Run 2 <0.0Example 4 Wipe - Run 1 <1.6 >99.99% >4.9 Example 4 Wipe - Run 2 <1.6Example 4 Overspray - Run 1 <1.7 >99.99% >4.9 Example 4 Overspray - Run2 <1.7

TABLE 5 Pseudamonas Aeruginosa Log₁₀ Average CFU/ Average % Log₁₀Example Test Carrier Reduction Reduction Example 3 Carrier - Run 10.3 >99.9999%  >6.9 Example 3 Carrier - Run 2 <0.0 Example 3 Wipe - Run1 <1.6 >99.999% >5.6 Example 3 Wipe - Run 2 1.6 Example 3 Overspray -Run 1 2 >99.999% 5.3 Example 3 Overspray - Run 2 1.7 Example 4 Carrier -Run 1 <0.0 >99.9999%  >6.9 Example 4 Carrier - Run 2 0.6 Example 4Wipe - Run 1 <1.6 >99.999% >5.6 Example 4 Wipe - Run 2 <1.6 Example 4Overspray - Run 1 2.3  >99.99% 4.7 Example 4 Overspray - Run 2 2.6

TABLE 6 VRE Log₁₀ Average CFU/ Average % Log₁₀ Example Test CarrierReduction Reduction Example 3 Carrier - Run 1 1.51 >99.9999%  >5.9Example 3 Carrier - Run 2 <0.0 Example 3 Wipe - Run 1 <1.6 >99.999% >5.1Example 3 Wipe - Run 2 <1.6 Example 3 Overspray - Run 1 <1.7 >99.99% >4.9 Example 3 Overspray - Run 2 <1.7 Example 4 Carrier - Run 10.3 >99.9999%  >6.5 Example 4 Carrier - Run 2 <0.0 Example 4 Wipe - Run1 <1.6 >99.999% >5.1 Example 4 Wipe - Run 2 <1.6 Example 4 Overspray -Run 1 <1.7  >99.99% >4.9 Example 4 Overspray - Run 2 <1.7

TABLE 7 MRSA Log₁₀ Average CFU/ Average % Log₁₀ Example Test CarrierReduction Reduction Example 3 Carrier - Run 1 0.9 >99.9999%  >6.2Example 3 Carrier - Run 2 <0.0 Example 3 Wipe - Run 1 <1.6 >99.999% >5.1Example 3 Wipe - Run 2 <1.6 Example 3 Overspray - Run 1 4.7  >99.9% >3.5Example 3 Overspray - Run 2 <1.7 Example 4 Carrier - Run 1 1.58 >99.999%5.2 Example 4 Carrier - Run 2 1.38 Example 4 Wipe - Run 1<1.6 >99.999% >5.1 Example 4 Wipe - Run 2 <1.6 Example 4 Overspray - Run1 6.6  >99.7% >2.5 Example 4 Overspray - Run 2 <1.7

The results shown in Tables 3-7 illustrate the efficacy of the spraybottle of the present disclosure for removing and killing a variety ofmicroorganisms. For the majority of the results, the sprayed carrier(without wiping), the wiped carrier, and the oversprayed carrier eachprovided an antimicrobial efficacy greater than 99.999% for each of thetested microorganisms. Several of the overspray runs, such as theoverspray runs in Table 7, exhibited high levels of variability betweenthe Run 1 and Run 2. The higher CFU/carriers are believed to be due toimproper priming of the spray bottles prior to spraying the treatedcarriers.

13.4 Examples 5 and 6: Antimicrobial Efficacy

The efficacy of spray bottles of Examples 5 and 6 in reducingconcentrations of Influenza A (H1N1) virus was also measured. Theexperiment was performed pursuant to ASTM E1053-02 and ASTM E1482-04,where samples of treated carriers contained Influenza A (H1N1) virus(ATCC #VR-1469). The treated carriers were also loaded with 5% fetalbovine serum to function as an organic soil load.

The spray bottles of Examples 5 and 6 were the same as the spray bottleof Example 1, described above, where the spray bottles of Examples 5 and6 were also filled with tap water for the experiment. The test methodwas modified by spraying the treated carriers for six seconds with thespray bottles of Examples 5 and 6 at a distance of ranging from three tofour inches from the treated carriers, and with an ambient temperatureof 24° C.

Following the exposure time, the plates were individually scraped with acell scraper to re-suspend the contents. A 10.6 milliliter aliquot ofvirus-test substance mixture was recovered from the plate sprayed withthe spray bottle of Example 5, and a 11.5 milliliter aliquot ofvirus-test substance mixture was recovered from the plate sprayed withthe spray bottle of Example 6. The recovered mixtures were divided inhalf and immediately passed through two Sephadex gel filtration columnsper unit utilizing the syringe plungers in order to detoxify themixtures. The filtrates of each test unit were then pooled and titeredby 10-fold serial dilution and assayed for infectivity and/orcytotoxicity.

All cell controls were negative for test virus infectivity. The titer ofthe input virus control was 7.5 log₁₀. The titer of the dried viruscontrol was 6.5 log₁₀. Following exposure to the sprays from the spraybottles of Examples 5 and 6, test virus infectivity was not detected inthe virus-test substance mixture for either lot at any dilution tested(≦1.2 log₁₀ for Example 5, and ≦1.3 log₁₀ for Example 6). Test substancecytotoxicity was also not observed in either lot at any dilution tested(≦1.2 log₁₀ for Example 5, and ≦1.3 log₁₀ for Example 6).

The neutralization control (non-virucidal level of the test substance)indicated that the test substance was neutralized at ≦1.2 log₁₀ forExample 5, and ≦1.3 log₁₀ for Example 6. Taking the cytotoxicity andneutralization control results into consideration, as well as the volumeof test substance recovered following the exposure time, the reductionin viral titer was ≧5.3 log₁₀ for Example 5 and ≧5.2 log₁₀ for Example6. Accordingly, under the conditions of tests and in the presence of a5% fetal bovine serum soil load, the spray bottles of Examples 5 and 6demonstrated complete inactivation of Influenza A (HINI) virus.

13.5 Examples 7 and 8: Antimicrobial Efficacy

The efficacy of spray bottles of Example 7 and 8 in reducing bacteriaconcentrations was also measured. The experiment was performed pursuantto the U.S. Environmental Protection Agency (EPA) AOAC Germicidal SprayMethod. Separate samples of treated carriers contained MRSA, E. coli,Listeria, Pseudomonas, Salmonella, E. coli O157:H7, and VRE.

The spray bottles of Examples 7 and 8 were the same as the spray bottleof Example 1, described above, where the spray bottles of Examples 7 and8 were also filled with tap water for the experiment. For each test runfor Examples 7 and 8, the test method was modified by spraying thetreated carriers for six seconds with the given spray bottle for sixseconds with the spray bottle at a distance of ranging from three tofour inches from the treated carriers. One-third of the treated carrierswere then wiped after being sprayed with a wipe to simulate a wipingaction, where the wipe used was commercially available under the tradedesignation “WYPALL” All Purpose Wipes from Kimberly-Clark Corporation,Neenah, Wis. Another third of the treated carriers remained unwiped tomeasure the efficacy of the spray itself. The final third of the treatedcarriers were oversprayed, which involved spraying a fine mist in theair, which then deposited onto the treated carriers.

Each spray bottle test for Examples 7 and 8 was duplicated. In otherwords, the spray bottle of Example 7 was tested in two runs, and thespray bottle of Example 8 was tested in two runs. Tables 8 and 9illustrate the antimicrobial efficacy of the spray bottle of Example 7against the bacteria for Runs 1 and 2, respectively. Correspondingly,Tables 10 and 11 illustrate the antimicrobial efficacy of the spraybottle of Example 8 against the bacteria for Runs 1 and 2, respectively.

TABLE 8 Example 7 - Run 1 Microorganism Carrier Wipe Overspray MRSA100.00% 100.00% poor E. coli 100.00% 100.00% 100.00% ListeriaMonocytogenes 99.99% 99.99% poor Pseudamonas Aeruginosa 100.00% 100.00%100.00% Salmonella Enteritidis 100.00% 99.99% 99.99% E. coli O157:H7100.00% 100.00% 100.00% VRE 100.00% 100.00% poor

TABLE 9 Example 7 - Run 2 Microorganism Carrier Wipe Overspray MRSA100.00% 100.00% 100.00% E. coli 100.00% 100.00% 100.00% ListeriaMonocytogenes 99.99% 99.99% 99.99% Pseudamonas Aeruginosa 100.00%100.00% 100.00% Salmonella Enteritidis 100.00% 99.99% 99.99% E. coliO157:H7 100.00% 100.00% 100.00% VRE 100.00% 100.00% 100.00%

TABLE 10 Example 8 - Run 1 Microorganism Carrier Wipe Overspray MRSA100.00% 100.00% 100.00% E. coli 100.00% 100.00% 100.00% ListeriaMonocytogenes 100.00% 99.99% 99.99% Pseudamonas Aeruginosa 100.00%100.00% 100.00% Salmonella Enteritidis 100.00% 99.99% 99.99% E. coliO157:H7 100.00% 100.00% 100.00% VRE 100.00% 100.00% 100.00%

TABLE 11 Example 8 - Run 2 Microorganism Carrier Wipe Overspray MRSA100.00% 100.00% poor E. coli 100.00% 100.00% 100.00% ListeriaMonocytogenes 100.00% 99.99% 99.99% Pseudamonas Aeruginosa 100.00%100.00% poor Salmonella Enteritidis 100.00% 99.99% 99.99% E. coliO157:H7 100.00% 100.00% 100.00% VRE 100.00% 100.00% poor

The results shown in Tables 8-11 further illustrate the efficacy of thespray bottle of the present disclosure for removing and killing avariety of different bacteria. As shown, the spray carrier and thespray/wiping combination each provided an antimicrobial efficacy of99.999% for each of the tested bacteria. Furthermore, the results of theoverspray provided an antimicrobial efficacy of 99.99% for most of thetested bacteria. The samples that provided poor antimicrobial efficaciesare believed to be due to a lack of conductivity due to the overspray,which effectively eliminates the conductive conduit. This further showsthat the conductivity generated from the spray bottle is providing theantimicrobial activity, rather than the water or solution produced fromthe electrolysis cell.

13.6 Examples 9-11: Antimicrobial Efficacy

The efficacy of spray bottles of Example 9-11 in reducing bacteriaconcentrations was also measured pursuant to the same proceduredescribed above for Example 2, except that the sprayed samples were notwiped. Separate samples of treated carriers contained E. coli O157:H7,Salmonella enteritidis, and Listeria monocytogenes. In comparison to thespray bottle of Example 2, which was filled with tap water, the spraybottles of Examples 9-11 were filled with water having different mineralconcentrations. Tables 12-14 list the types of water supplied duringvarious runs with the spray bottles of Examples 9-11 and with the spraybottle of Comparative Example A. The spray bottle of Comparative ExampleA incorporated an electrolysis cell for electrochemically activating thewater, but did not include an electroporation electrode for generatingand electric field through the sprayed water.

The “Bottled Water with Salt” was a mixture of 0.25% by volume sodiumchloride in bottled water commercially available under the tradedesignation “FIJI” Natural Artesian Water from FIJI Water Company, LLC,Los Angeles, Calif. The “Tap Water” was standard tap water attained inMinneapolis, Minn. The “Tap Water with Salt” was a mixture of 0.25% byvolume sodium chloride in the Tap water. The “Distilled Water” was astandard distilled water. Tables 12-14 illustrate the antimicrobialefficacy of the spray bottles of Examples 9-11 against E. coli O157:H7,Salmonella enteritidis, and Listeria monocytogenes, respectively.

TABLE 12 E. coli O157:H7 Bottle Water Tap Tap Water Distilled Examplewith Salt Water with Salt Water Comparative   99%    0%  99.9%   0%Example A Example 9 99.999% 99.999% 99.999% 99.9% Example 10 99.999%99.999% 99.999% 99.9% Example 11 99.9999%  99.999% 99.999% 99.9%

TABLE 13 Salmonella Enteritidis Bottle Water Tap Tap Water DistilledExample with Salt Water with Salt Water Comparative  99.9%  99.9%  99.9%  0% Example A Example 9 99.999% 99.99%  99.99% 99.99% Example 1099.999% 99.99% 99.999% 99.99% Example 11 99.999% 99.99% 99.999% 99.99%

TABLE 14 Listeria Monocytogenes Bottle Water Tap Tap Water DistilledExample with Salt Water with Salt Water Comparative  99.99%   99% 99.99%   0% Example A Example 9 99.9999% 99.999% 99.9999% 99.99%Example 10 99.9999% 99.999% 99.9999% 99.99% Example 11 99.9999% 99.999%99.9999% 99.99%

Each of the tested samples for Examples 9-11 achieved greater than a99.99% reduction for each of the bacteria tested with the Bottled Waterwith Salt, the Tap Water, and the Tap Water with Salt, and exhibitedgreater killing efficacy compared to the results of Comparative ExampleA. This is particularly true with the Distilled Water, where the testedsamples of Comparative Example A was ineffective in reducing thebacteria. Accordingly, the electroporation attainable with the spraybottle of the disclosure is capable of effectively removing and killinga variety of bacteria from surfaces, regardless of the mineral contentof the water used with the spray bottle.

13.7 Example 12: Water Analysis

The water used in the spray bottle of Example 1 was also measured toidentify its pH, conductivity, and the concentrations of sodium,calcium, and magnesium ions in the water samples. The pH of the waterwas measured using a calibrated pH probe and meter. The conductivity ofthe water was measured using a calibrated one-centimeter conductivityprobe and meter. The concentrations of the sodium, calcium, andmagnesium ions in the water were determined using an Inductively CoupledPlasma—Atomic Emission Spectrometer pursuant to EPA Method 200.7.Additionally, the Total Hardness of the water was calculated from thedetermined calcium and magnesium concentrations pursuant to Equation 1:

Total Hardness=2.497*[calcium]+4.116*[magnesium]  (Equation 7)

where the Total Hardness of the water is in milligrams/liter (mg/L) ofCaCO₃, [calcium] is the concentration of calcium in the water in mg/L,and [magnesium] is the concentration of magnesium in the water in mg/L.Table 15 illustrates the measured pH, conductivity in microSiemens (μS),concentrations of sodium, calcium, and magnesium ions inparts-per-million (ppm), and the Total Hardness of the water in ppm.

TABLE 15 Property Results pH 7 Conductivity 1280 μS Sodium concentration167 ppm Calcium concentration 19 ppm Magnesium concentration 6 ppm TotalHardness 73 ppm CaCO₃

14. Example Uses in Various Industries

One or more of the examples and embodiments disclosed herein, ormodifications thereof, can be implemented in the following industriesand/or applications, which are provided as non-limiting examples:

A. Industrial Cleaning & Disinfection:

Surface Cleaning & Disinfection Removal of Bio-Film & Algae EffectiveBiocide Clean-in-Place [CIP] Sanitizing & Disinfection

B. Health & Medical Care:

Cold Sterilization of Medical Instruments Surface Cleaning &Disinfection. Production of Sterile Water

Linen disinfection when washed

Fogging Disinfection of Air & Clean Rooms

C. Veterinarian Applications:

Increased vitality and disease resistanceResidue-free treatment of Infection and wound careIncreased nutritional benefit of food

D. Poultry Industry:

General Disinfection. Surface Cleaning & Fog Misting Medium for AerobicBacteria

Elimination of pathogens in drinking waterLice & Other Pest Control on feathersFog Misting to destroy Aerobic & Anaerobic Bacteria.Equipment cleaning without further additives

E. Horticulture/Agriculture:

Suppression of Pathogenic Fungi on Plants Disinfection of IrrigationWater for Crop Spraying & Pest Control.

Decreased Toxicity of Effluent Filtration into Water Aquifers

Prolonged Shelf-Life of Vegetables, Fruit & Cut Flowers

Disinfection of seeds, stimulation and acceleration of plant growth withincreased yield

Disinfection of Stored Grain

F. Water, Waste Water & Sewage Treatment.

Disinfect Municipal Effluent Neutralize Water Removal of Bio-Film &Algae Neutralize Odor Compounds Reduce Formation of Toxic By-Products.15. Further Suspension Mechanisms

Another aspect of the disclosure relates to a process for deactivatingor destroying microorganisms, by applying a potential or electrochemicalpressure to microorganisms, in a medium that is capable of suspendingthe microorganisms using alternative and/or additional suspensionmechanisms. As discussed above, such as for spray bottles 10, 300, 500and/or any of the other apparatus 1200, 1300, 1400, 1500 describedherein, microorganism suspension can be accomplished withelectrochemically-activated liquids produced by one or more electrolysiscells. In addition, microorganisms can be suspended in the medium (e.g.,a liquid) with use of chemical compounds, such as suspension additives(e.g., detergent surfactants), liquid-activating materials (e.g.,zeolites), and the like. As discussed below, these materials areconfigured to treat a liquid to increase its suspension properties. Thesuspension additive(s) can be used in addition to or in replace of anelectrolysis cell for promoting increased suspension of microorganismsin the liquid distributed from the apparatus, for example.

15.1 Suspension Additives

FIG. 21 is a diagram illustrating system 1700 according to an exampleembodiment of the disclosure, which can be incorporated into any of theembodiments disclosed herein, for example. System 1700 includeselectrical subsystem 1700 a and fluid subsystem 1700 b, where electricalsubsystem 1700 a may function in the same manner as system 1600 (shownin FIG. 19), for example, and where the corresponding reference labelsare increased by “100”. In the embodiment shown in FIG. 20, however, thecomponent corresponding to electrolysis cell 1606 is replaced with pump1726 for feeding a suspension additive from reservoir 1728 to mixingchamber 1730. This arrangement also allows pump 1708 to feed a liquid(e.g., tap water) from reservoir 1732 to mixing chamber 1730 to mix thesuspension additive in the liquid. The components corresponding to LEDs1622 and 1624 are omitted in FIG. 20 for ease of discussion. Thesuspension additive may be added to the liquid at any other locationalong the liquid flow path, such as directly in reservoir 1732, and maybe mixed by any suitable method, with or without a pump, and/or suppliedas part of the liquid introduced into reservoir 1732, for example.

The suspension additive (such as that in reservoir 1728) desirablyincludes one or more chemical compounds configured to assist insuspending particles and microorganisms in the liquid dispensed fromreservoir 1732. As discussed above, the suspension mechanism may alterthe ORP of the dispensed liquid (producing dispensed liquid having apositive ORP, a negative ORP or a combination of both). These enhancedcleaning effects can serve to suspend particles and microorganisms abovethe surface within the dispensed liquid, for example. Suitable chemicalcompounds for use in the suspension additive include, for example,compounds configured to reduce the surface tension of the liquid, suchas surfactants (e.g., detergent surfactants).

Examples of suitable surfactants for use in the suspension additiveinclude anionic, non-ioninic, and cationic surfactants. Examples ofanionic surfactants include alkyl sulfates, alkyl sulfonates,sulfosuccinates, and combinations thereof. Examples of suitable alkylsulfates include primary and secondary alkyl sulfates, alkyl ethersulphates, fatty alcohol sulfates, and combinations thereof. Examples ofsuitable alkyl chain lengths for the alkyl sulfates range from C8 to C15(e.g., C8 to C15 primary alkyl sulphates). Examples of suitable alkylsulfonates include alkyl benzene sulfonates (e.g., linear alkyl benzenesulfonates with C8 to C15 alkyl chain lengths), alkyl xylene sulfonates,fatty acid ester sulfonates, and combinations thereof. Examples ofsuitable sulfosuccinates include dialkyl sulfosuccinates.

Examples of nonionic and cationic surfactants include alcoholethoxylates (e.g., alkyl phenoxy polyethoxy ethanols), alkylpolyglycosides, polyhydroxyamides, monoethanolamine, diethanolamine,triethanolamine, glycerol monoethers, alkyl ammonium chlorides, alkylglucosides, polyoxyethylenes, and combinations thereof.

The suspension additive may also include one or more additionalmaterials to assist in the suspension and cleaning properties. Examplesof suitable additional materials include oxidants, enzymes, defoamingagents, colorants, optical brighteners, corrosion inhibitors, perfumes,antimicrobial agents, anitbacterial agents, antifungal agents, pHmodifiers, solvents, and combinations thereof. The additive materialsmay provide longer residence times and greater sanitizing effect on somesurfaces, such as porous surfaces. For example, the additive materialsmay reside on a surface after the electric field (from electroporationelectrode 1714) is removed.

The suspension additive may be provided to reservoir 1728 (and/orreservoir 1732) in a variety of media, for example fluids, solutions,pellets, blocks, powders, and the like. In the shown embodiment, thesuspension additive is desirably a solution of the surfactant(s) andadditional materials dissolved or otherwise suspended in a carriermedium (e.g., water).

During operation, when trigger 1720 is depressed, control electronics1704 is enabled and generates appropriate voltage outputs for drivingpumps 1708 and 1726 and electroporation electrode 1714. The relativefeed rates of pumps 1708 and 1726 may vary depending on the desiredconcentration of the suspension additive in the liquid. Each of thepumps may include, for example, a controller that controls the operationof the pump through a control signal, for example. In accordance withone exemplary embodiment, the control signal can include a pulsed signalthat provides power relative to ground and controls the duration overwhich the pump drives the suspension additive through mixing chamber1730. Other types of control signals and control loops (open or closed)can be used. In addition, one or both of pumps 1726 and 1708 can beeliminated and the liquid and/or suspension additive can be fed byanother mechanism, such as gravity. In addition, the operation of pumpsmay be monitored by current sensors 1710 and 1712, for example.

As discussed above, the suspension additive and the liquid are combined(such as in mixing chamber 1730) to form a solution. Mixing chamber 1730may include a variety of geometries and designs configured to assist inthe mixing process (e.g., baffled walls). Other examples of suitablemixing devices includes a Venturi tube and merging flow paths. Therelative concentrations of surfactant(s) in the suspension additive(such as from reservoir 1728) and the liquid from reservoir 1732 mayvary on the concentration of the surfactant(s) in the suspensionadditive and the relative feed rates, for example. Accordingly, uponexiting mixing chamber 1730 (and/or from a pre-mixed solution fromreservoir 1732), the solution desirably includes a surfactantconcentration that is great enough to suspend particles and/ormicroorganisms in the dispensed solution. Examples of suitablesurfactant concentrations in the solution upon exiting mixing chamber1730 (and/or reservoir 1732) range from about 0.1% by volume to about15% by volume, with particularly suitable surfactant concentrationsranging from about 0.5% to about 10% by volume.

The resulting solution may exit mixing chamber 1730 (and/or reservoir1732 for example) and come into contact with electroporation electrode1714 prior to being dispensed (e.g., sprayed) onto a surface or volumeand/or upon being dispensed. The suspension additive can serve tosuspend particles and microorganisms above the surface within thedispensed solution. In particular, while not wishing to be bound bytheory, it is believed that at least a portion of the surfactant(s) ofthe suspension additive, which contain hydrophobic and hydrophilicmolecular chain ends, can reside at the liquid/surface/gas interfaces.As such the hydrophilic chain ends reside within the liquid and thehydrophobic chain ends extend out of the liquid, thereby reducing thesurface tension of the liquid. When the hydrophobic chain ends contactparticles and microorganisms on the surface, they can entrap and suspendthe particles/microorganisms above the surface within the dispensedsolution. Furthermore, in some embodiments, the surfactants can increasethe potency of the liquid, and assist in penetrating the structures ofthe microorganisms.

As discussed above, electroporation electrode 1714 may apply an electricfield through the solution to the surface, which can be sufficient tocause irreversible electroporation of (or otherwise inactivate ordamage) the suspended microorganisms. A suspension additive in thesolution allows the microorganisms to be suspended above the surface inthe same or similar manner to an altered ORP that is achieved with anelectrolysis cell, for example. By separating the microorganisms fromthe surface, for example, such that they are suspended in the solutionabove the surface, the electric field produced along the surface byelectroporation electrode 1714 is applied more easily across themicroorganism cells. Whereas, if the microorganism is in contact withthe surface, the electric field is more easily discharged into thesurface ground and may be less effective in creating irreversibleelectroporation of the organisms cells. With the cell suspended, theapplied alternating field, for example, oscillates back and forthcausing damage to the cells.

While illustrated in use with system 1700, suspension additives may beused with any of the embodiments of the disclosure. For example, thesuspension additive may be introduced into reservoir 12 of spray bottle10 (shown in FIG. 1) and in container 510 of spray bottle 500 (shown inFIGS. 10A-10C) in a batch manner when filling reservoir 12 with theliquid (and/or supplied from a separate reservoir carried by theapparatus). Furthermore, system 1700 may also be used in cleaner 1200(shown in FIG. 15), surface cleaning assembly 1300 (shown in FIG. 16),flat mop 1400 (shown in FIG. 17), device 1500 (shown in FIG. 18), system1600 (shown in FIG. 19), and the like. In these embodiments, theelectrolysis cells (e.g., electrolysis cells 18, 552, 1208, and 1606)may be omitted. Alternatively, the electrolysis cells may be used inconjunction with the suspension additive to further increase thesuspension of particles and microorganisms in the dispensed solution.

15.2 Liquid-Activating Materials

FIG. 22 is a schematic illustration of spray bottle 1810, which is anexample of a hand-held spray device that is configured to retain one ormore liquid-activating materials (e.g., zeolites) for altering the ORPof liquids retained and dispensed by spray bottle 1810. In anotherexample, the spray device may form part of a larger device or system. Inthe embodiment shown in FIG. 22, spray bottle 1810 includes reservoir1812, which is defined by a base housing of spray bottle 1810, and isconfigured to contain a liquid to be treated and then dispensed throughnozzle 1814. Additionally, reservoir 1812 may contain filter 1816 andmedia 1818, where media 1818 compositionally includes one or moreliquid-activating materials. Filter 1816 is a media filter configured toallow the liquid to pass through, but desirably prevents the macrosizedparticles of media 1818 from passing through. Reservoir may, forexample, be configured as a replaceable cartridge that is engageable anddisengageable with 1820.

Examples of suitable liquid-activating materials for use in media 1818include porous minerals, such as porous aluminosilicate minerals (e.g.,zeolites). Examples of suitable zeolites for use in media 1818 includehydrated and anhydrous structures of aluminosilicate minerals, which maycontain one or more of sodium (Na), potassium (K), cerium (Ce), calcium(Ca), barium (Ba), strontium (Sr), lithium (Li), and magnesium (Mg).Examples of suitable zeoiltes for use in media 1818 include analcime,amicite, barrerite, bellbergite, bikitaite, boggsite, brewsterite,chabazite, clinoptilolite, cowlesite, dachiardite, edingtonite,epistilbite, erionite, faujasite, ferrierite, garronite, gismondine,gobbinsite, gmelinite, gonnardite, goosecreekite, harmotome, heulandite,laumontite, levyne, mazzite, merlinoite, montesommaite, mordenite,mesolite, natrolite, offretite, paranatrolite, paulingite, perlialite,phillipsite, pollucite, scolecite, stellerite, stilbite, thomsonite,tschernichite, wairakite, wellsite, willhendersonite, yugawaralite,anhydrous forms thereof, and combinations thereof. Examples ofcommercially available zeolites for use in media 1818 includeclinoptilolites from KMI Zeolite, Inc., Sandy Valley, Nev., which havean average density of about 2.3 grams/cubic-centimeter and a nominalparticle sizing of +40 mesh.

Non-zeolite materials or mechanisms may also be utilized. Examples ofsuitable non-zeolite minerals for use in media 1818 include resins,apophyllite, gyrolite, hsianghualite, kehoeite, lovdarite, maricopaite,okenite, pahasapaite, partheite, prehnite, roggianite, tacharanite,tiptopite, tobermorite, viseite, and combinations thereof. Examples ofsuitable resins include ion-exchange resins, such as those havingcross-linked aromatic structures (e.g., cross-linked polystyrene)containing active groups (e.g., sulfonic acid groups, amino groups,carboxylic acid groups, and the like). The ion-exchange resins may beprovided in a variety of media, such as in resin beads, for example.These non-zeolite minerals may be used in combination with or asalternatives to the zeolites in media 1818.

Media 1818 may be provided in a variety of media forms, such as inceramic balls, pellets, powders, and the like. While retained inreservoir 1812, media 1818 treats the retained liquid, thereby impartinga negative ORP (and/or a positive ORP) on the retained liquid by ionexchange, for example. Media 1818 desirably imparts a negative ORP tothe liquid of at least about of −50 mV and/or a positive ORP of at leastabout +50 mV. In another example, media 1818 imparts a negative ORP tothe liquid of at least about of −100 mV and/or a positive ORP of atleast about +100 mV. As discussed above, altering the ORP allows thedispensed treated liquid to suspend particles and microorganisms.

Spray bottle 1810 also includes cap housing 1820, tube 1822, pump 1824,actuator 1826, electroporation electrode 1828, circuit board and controlelectronics 1830, and batteries 1832. Cap housing 1820 desirably sealsreservoir 1812 when closed, and may be depressed in the direction ofarrow 1834 by a user to engage actuator 1826. Batteries 32 can includedisposable batteries and/or rechargeable batteries, for example, orother appropriate portable or corded electrical source in addition to orin place of batteries, to provide electrical power to electroporationelectrode 1828 when energized by circuit board and control electronics30. In one embodiment, pump 1824 may also be electrically powered.

Pump 1824 draws liquid from reservoir 1812 through filter 1816 and tube1822, and forces the liquid out nozzle 1814. While passing throughnozzle 1814, the liquid contacts electroporation electrode 1828. Asdiscussed above, electroporation electrode 1828 may apply a voltage(such as an alternative voltage) to the dispensed solution, creating anelectric field through the dispensed solution to the surface, which canbe sufficient to cause damage to the suspended microorganisms, such asby irreversible electroporation. The altered ORP of the dispensed liquidallows the microorganisms to be suspended above the surface in the sameor similar manner to an altered ORP that is achieved with anelectrolysis cell, for example. By suspending the microorganisms fromthe surface, for example such that they are suspended in the solutionabove the surface, the electric field produced along the surface byelectroporation electrode 1828 is applied more easily across themicroorganism cells. With the cell suspended, the applied alternatingfield oscillates back and forth causing damage to the cells, asdiscussed above.

While illustrated in use with system 1810, media 1818 may be used withany of the embodiments of the disclosure. For example, the suspensionadditive may be introduced into reservoir 12 of spray bottle 10 (shownin FIG. 1) and in container 510 of spray bottle 500 (shown in FIGS.10A-10C) in a batch manner, for example, when filling reservoir 12 withthe liquid. In these embodiments, the electrolysis cells (e.g.,electrolysis cells 18 and 552) may be omitted. Alternatively, theelectrolysis cells may be used in conjunction with media 1818 to furtherincrease the suspension of particles and microorganisms in the dispensedsolution.

In a further example, the reservoir 1812 may include a fill port oropening that may be used to fill (and/or refill) the reservoir with theliquid and/or media 1818. In yet a further example, bottle 1810 mayinclude a fitting for receiving liquid from an external source, such asthrough a hose, wherein the liquid flows through media 1818.

Furthermore, media 1818 may also be used in cleaner 1200 (shown in FIG.15), surface cleaning assembly 1300 (shown in FIG. 16), flat mop 1400(shown in FIG. 17), device 1500 (shown in FIG. 18), system 1600 (shownin FIG. 19), and the like.

FIG. 23 is a schematic diagram of a cartridge 1900 that may beinstalled, for example, in a fluid line of a flow-through system, suchas between fluid line segments 1902 and 1904. Cartridge 1900 may bepositioned at any suitable location along the flow paths on any of theapparatus described herein, such as cleaner 1200 (shown in FIG. 15),surface cleaning assembly 1300 (shown in FIG. 16), flat mop 1400 (shownin FIG. 17), device 1500 (shown in FIG. 18), system 1600 (shown in FIG.19), spray bottle 10 (shown in FIG. 1), spray bottle 300 (shown in FIG.8), spray bottle 500 (shown in FIGS. 10A-10C), and spray bottle 1810(shown in FIG. 22).

In the embodiment shown in FIG. 23, cartridge 1900 includes housing1906, which defines interior chamber 1908, and interfaces 1910 and 1912.Interfaces 1910 and 1912 desirably allow cartridge 1900 to materespectively with fluid line segments 1902 and 1904 in a manner that islockable and unlockable, or otherwise removably engagable. Thisarrangement allows multiple cartridges to interchangably mate with fluidline segments 1902 and 1904. For example, when a cartridge 1900eventually expires over multiple uses, the expired cartridge 1900 may beremoved from fluid line segments 1902 and 1904, and replaced with afresh cartridge 1900. Interfaces 1910 and 1912 can also include simplemale and/or female fittings.

Interior chamber 1908 retains media 1914 for treating liquids passingthrough cartridge 1900 with the use of media filters 1916, where theflow of the liquids through cartridge is represented by arrows 1917).Suitable materials for media 1914 include those discussed above formedia 1818 (shown in FIG. 22), for example. Accordingly, media 1914treats the liquid flowing through interior chamber 1908, therebyimparting a negative ORP (and/or a positive ORP) on the flowing liquidby ion exchange. The volume of interior changer 1908 and the amount ofmedia 1914 within interior chamber 1908 are desirably selected toprovide a suitable residence time of the flowing liquid to sufficientlyalter the ORP. These parameters may vary depending on the volumetricflow rate of the liquid through fluid line segments 1902 and 1904. In afurther example, media 1914 is contained in one or more of the liquidreservoirs/tanks carried by the various apparatus described herein, suchas cleaner 1200 (shown in FIG. 15), surface cleaning assembly 1300(shown in FIG. 16), flat mop 1400 (shown in FIG. 17), device 1500 (shownin FIG. 18), system 1600 (shown in FIG. 19), and the like.

Media 1914 desirably imparts a negative ORP to the liquid of at leastabout of −50 mV and/or a positive ORP of at least about +50 mV, and inanother embodiment at least about of −100 mV and/or a positive ORP of atleast about +100 mV. As discussed above, altering the ORP allows thedispensed treated liquid to suspend particles and microorganisms. Thetreated liquid may then exit interior chamber 1908 into fluid linesegment 1904 to be dispensed from the system, such as discussed abovefor cleaner 1200, surface cleaning assembly 1300, flat mop 1400, device1500, system 1600, and the like.

Interchangeable cartridges or other supply containers of media 1818and/or 1914 may be configured in many different ways to engage with anddisengage from the particular apparatus with which it is used. Forexample, with the spray bottle embodiments of the disclosure, the basehousings of spray bottles 10, 500 and 1810 (respectively containingreservoir 12, container 510, reservoir 1812) may be removably engageablewith the head portion (and/or any other portion) of the respective spraybottle, thereby allowing multiple cartridge base portions tointerchangably mate with a single head portion. In another example, anypart of the spray bottles, such as the base portions or head portionsmay be configured to removably engage a cartridge of media 1818 and/or1914. In a further example, the spray bottle can be configured to engagesuch a cartridge within the base of the bottle or at the head of thebottle, such as at base 502 and/or at the location of electrolysis cell552 in the head portion of spray bottle 500 shown in FIGS. 10A-10C. Thereplaceable cartridges may be configured to allow multipleinterchangeable cartridges to readily mate with, and disengage from, thefluid lines of the spray bottle, for example.

In one particular example, the base of a spray bottle is configured toreceive a cylindrical cartridge containing media 1818, 1914. Forexample, looking at FIG. 1, the reservoir 12 of bottle 10 (shown inFIG. 1) can be modified to eliminate electrolysis cell 18 and to includea circular opening within the base of the reservoir to receive acylindrical cartridge. One end of the cylindrical cartridge isinsertable along its longitudinal axis into the opening. The oppositeend may include an appropriate latch and sealing mechanism. For example,the bottom end of the cartridge may have an annular shoulder with ano-ring that seals against the bottom of reservoir 12, about acircumference of the opening, when the cylindrical cartridge is fullyinserted into the reservoir so as to seal the interior of the reservoirabout the base of the cylindrical cartridge. The length of the cartridgemay extend into the reservoir by any suitable distance, such as but notlimited to half or a third of the height of the reservoir. The cartridgecan have any suitable mechanism to lock the cartridge into place, suchas by rotating the cartridge about its axis upon insertion. Examplesinclude mating threads and other locking mechanisms.

The walls of the cylinder can have any suitable configuration to permitinteraction between the media 1818, 1914 contained within the cartridgeand the liquid contained in the reservoir. For example, the cylinder mayinclude one or more apertures sufficient to allow the liquid to passinto the interior cavity of the cylindrical cartridge. In a particularexample, the side walls have a plurality of apertures formed by openingsin a mesh, screen, and/or perforated side wall, for example.

The apertures may be closed, for example, when not in use, such asbefore insertion, to reduce potential contamination of the mediacontained in the cartridge. In one example, the cartridge may besupplied with a removable film or sleeve that covers the aperturesduring storage. This film or sleeve may be removed prior to (or after)insertion of the cartridge into the base of the bottle. In anotherexample, the cartridge is configured with a sealing mechanism thatautomatically seals the one or more apertures when the cartridge is notinserted into and/or engaged with the bottle. For example, the cartridgemay include an inner cylindrical side wall and an outer cylindricalsleeve that is coaxial with and movable relative to the innercylindrical side wall. The inner cylindrical side wall contains themedia 1818, 1914 and has the one or more apertures discussed above. Theouter cylindrical sleeve is movable, such as in a circumferential oraxial direction, between a closed position and an open position. In theclosed position, the cylindrical sleeve covers one or more of theapertures of the inner cylindrical side wall so as to seal the interiorcavity of the cartridge from contamination, for example. In the openposition, the outer cylindrical sleeve uncovers one or more of theapertures in the inner cylindrical side wall. For example, the outercylindrical sleeve covers one or more of the apertures of the innercylindrical side wall so as to seal the interior cavity of the cartridgefrom contamination, for example. In one embodiment, the cylindricalouter sleeve includes a plurality of apertures that align with theapertures in the inner cylindrical side walls when in the open position.In the closed position, the apertures in the outer cylindrical sleeve donot align with the apertures in the inner cylindrical side wall suchthat the material of one cylinder seals or otherwise covers theapertures in the other cylinder. Many other arrangements andconstructions for engaging a cartridge with a reservoir are possible andcontemplated in the present disclosure.

Movement between the open and closed position may be manual orautomatic, for example. In one embodiment, the outer sleeve is biasedinto the closed position, by a mechanism, such as a spring action. Uponinsertion into the reservoir, the outer sleeve is biased into the openposition, such by a lever or surface engagement with the reservoir orother element, for example.

Similarly, in embodiments in which media 1818, 1914 is used in apparatussuch as cleaner 1200 (shown in FIG. 15), surface cleaning assembly 1300(shown in FIG. 16), flat mop 1400 (shown in FIG. 17), device 1500 (shownin FIG. 18), system 1600 (shown in FIG. 19), and the like, the media maybe contained in replaceable cartridges, for example. These cartridgesmay be configured to allow multiple interchangeable cartridges toreadily mate with, and disengage from, the fluid lines of the apparatus.For example, the cartridge may be accessible/insertable from an interiorof the apparatus or from an exterior of the apparatus. In one example,the cartridge is accessible/insertable through a side wall of theapparatus.

In embodiments incorporating media 1818 and/or media 1914, for example,electrolysis cells (e.g., electrolysis cells 18, 552, 1208, and 1606)may be omitted. Alternatively, the electrolysis cells may be used inconjunction with a further suspension mechanism to further increase thesuspension of particles and microorganisms in the dispensed solution.The use of further (or alternative) suspension mechanisms, such assuspension additives (e.g., detergent surfactants) and liquid-activatingmaterials (e.g., zeolites), increases the versatility of the systemsdiscussed herein for suspending particles and microorganisms indispensed liquids for use with a sanitization process such as, forexample, by electroporation.

An aspect of the disclosure relates to an apparatus comprising: acontainer configured to engage a liquid and at least one compoundconfigured to increase suspension properties of the liquid to provide atreated liquid; a liquid flow path coupled to the container; a liquiddispenser coupled in the liquid flow path, adapted to dispense thetreated liquid to a surface or volume of space; an electrodeelectrically coupled to the liquid flow path; and a control circuitadapted to generate an alternating electric field between the electrodeand the surface or volume of space, through the dispensed treatedliquid, without a corresponding return electrode.

The container can include but is not limited to any suitable containersuch as various elements described herein as containers, reservoir,tanks, chambers, cartridges, compartments, etc, for example. Forexample, the container can include a liquid source container (forexample containers 12, 510, 1206, 1406, 1732, 1812), an additivecontainer (for example container 1728), a mixing chamber 1730, cartridge1900 (flow-through and/or source, for example), compartment 1408, etc.,merging fluid lines, etc.

The container may engage a liquid with at least one compound in anysuitable manner, including but not limited to active and/or passivemixing, blending, combining, etc.; containing; and/or enablinginteraction, contact and/or reaction between. For example, engagementmay include a pre-mixed solution of the liquid and the compound beingcontained in a container. In another example, the container may enable aliquid to engage a least one compound supplied from a separate source,such as in a mixing chamber, for example. In another example thecontainer may enable interaction between a liquid and at least onecompound within a flow-through and/or source cartridge. Otherarrangements are also envisioned.

At least one compound can include but is not limited to at least onesurfactant, at least one liquid-activating material. At least oneliquid-activating material can include, but is not limited to a materialselected from the group including zeolites, ion-exchange resins, andcombinations thereof.

Although the present disclosure has been described with reference to oneor more embodiments, workers skilled in the art will recognize thatchanges may be made in form and detail without departing from the scopeof the disclosure and/or the issued claims appended hereto. Also whilecertain embodiments and/or examples have been discussed herein, thescope of the invention is not limited to such embodiments and/orexamples. One skilled in the art may implement variations of theseembodiments and/or examples that will be covered by one or more issuedclaims appended hereto.

1. An apparatus comprising: an electrode, which lacks a correspondingreturn electrode of opposite polarity on the apparatus; and a controlcircuit electrically coupled to the electrode and configured to generateand apply to the electrode a voltage having a sinusoidal waveformcomprising at least one step on an edge of the waveform, wherein eachstep comprises a local peak, and wherein the apparatus is arranged togenerate an alternating electric field between the electrode and asurface or volume of space in response to the applied voltage.
 2. Theapparatus of claim 1, wherein the at least one step is located on atrailing edge of the sinusoidal waveform.
 3. The apparatus of claim 1,wherein the control circuit is configured such that the surface orvolume of space serves as a circuit ground for the alternating electricfield with respect to the electrode.
 4. The apparatus of claim 1,wherein the sinusoidal waveform comprises a frequency in a range ofabout 20 kilohertz to about 800 kilohertz and an alternating voltage ofabout 50 Volts rms to about 1000 Volts rms.
 5. The apparatus of claim 1,wherein: the frequency is in a range selected from the group consistingof between 20 KHz and 100 KHz, between 25 KHz and 50 KHz, between 30 KHzand 60 KHz, between 28 KHz and 40 KHz, and about 30 KHz; and the voltageis in a range selected from the group consisting of between 50 Volts rmsand 1000 Volts rms, between 500 Volts rms and 700 Volts rms, between 550Volts rms and 650 Volts rms, and about 600 Volts rms.
 6. The apparatusof claim 1, wherein: the frequency is in a range between 28 KHz and 40KHz; and the voltage is in a range of between 50 Volts rms and 1000Volts rms.
 7. The apparatus of claim 1, wherein the apparatus furthercomprises: a fluid flow path, wherein the electrode is electricallycoupled to the fluid flow path.
 8. The apparatus of claim 7, wherein thefluid flow path comprises an aqueous flow path.
 9. The apparatus ofclaim 1, wherein the apparatus further comprises: a liquid flow path,wherein the electrode is electrically coupled to the liquid flow path;and a dispenser coupled in the liquid flow path, adapted to dispenseliquid to the surface or volume of space.
 10. The apparatus of claim 9,wherein the electrode has an internal lumen through which the liquidflow path extends, and wherein at least a portion of the inner diametersurface of the electrode, which forms the internal lumen is electricallyconductive.
 11. The apparatus of claim 9, wherein the electrodecomprises an electrically conductive spray nozzle, which forms thedispenser.
 12. The apparatus of claim 1, further comprising: anelectrolysis cell in the liquid flow path and comprising electrolysiscell electrodes separated by an ion exchange membrane, wherein theelectrolysis cell electrodes are distinct from the electrode recited inclaim
 1. 13. The apparatus of claim 12, further comprising a secondcontrol circuit electrically coupled to the electrolysis cell, thesecond control circuit being distinct from the control circuit that iselectrically coupled to the electrode recited in claim
 1. 14. Theapparatus of claim 13 wherein the second control circuit is adapted toapply a DC voltage potential to the cell electrodes, and the controlcircuit that is electrically coupled to the electrode recited in claim 1is adapted to apply an AC voltage potential to that electrode.
 15. Theapparatus of claim 14, wherein a root-means square value of the ACvoltage potential is greater than a magnitude of the DC voltage.
 16. Theapparatus of claim 1, wherein the apparatus comprises a hand-held spraydevice, which comprises: a spray nozzle; and a liquid flow path leadingto the spray nozzle, wherein the electrode is electrically coupled tothe liquid flow path.
 17. The apparatus of claim 16, wherein thehand-held spray device comprises a hand-held spray bottle, whichcarries: the liquid flow path, the spray nozzle, the electrode and thecontrol circuit; a pump coupled in the liquid flow path; a container inthe liquid flow path for containing liquid to be dispensed by thenozzle; and a power source electrically connected to the controlcircuit.
 18. The apparatus of claim 1, wherein the apparatus comprises amobile floor surface cleaner, which comprises: a liquid flow path; aliquid dispenser coupled to the liquid flow path; a container in theliquid flow path for containing liquid to be dispensed by the liquiddispenser; at least one wheel configured to move the cleaner over asurface; a pump coupled in the liquid flow path; and a motor coupled todrive the at least one wheel.
 19. An apparatus comprising: a liquid flowpath; a liquid dispenser coupled in the liquid flow path; an electrodeelectrically coupled to the liquid flow path, which lacks acorresponding return electrode representing a circuit ground for theelectrode on the apparatus; and a control circuit coupled to theelectrode and configured to generate and apply to the electrode avoltage having a sinusoidal waveform comprising at least one step on anedge of the waveform, wherein each step comprises a local peak.
 20. Theapparatus of claim 19, wherein the at least one step is located on atrailing edge of the sinusoidal waveform.
 21. The apparatus of claim 19,wherein the apparatus is arranged to generate an alternating electricfield along liquid dispensed from the dispenser, between the electrodeand a surface or volume of space in response to the applied voltage andthe control circuit is configured such that the surface or volume ofspace serves as a circuit ground for the alternating electric field withrespect to the electrode.
 22. The apparatus of claim 19, wherein: thefrequency is in a range between 28 KHz and 40 KHz; and the voltage is ina range of between 50 Volts rms and 1000 Volts rms.
 23. The apparatus ofclaim 19, wherein the electrode has an internal lumen through which theliquid flow path extends, and wherein at least a portion of the innerdiameter surface of the electrode, which forms the internal lumen iselectrically conductive.
 24. The apparatus of claim 19, wherein theelectrode comprises an electrically conductive spray nozzle, which formsthe dispenser.
 25. The apparatus of claim 19, further comprising: anelectrolysis cell in the liquid flow path and comprising electrolysiscell electrodes separated by an ion exchange membrane, wherein theelectrolysis cell electrodes are distinct from the electrode recited inclaim
 19. 26. The apparatus of claim 25, further comprising a secondcontrol circuit electrically coupled to the electrolysis cell and beingconfigured to apply a DC voltage potential to the cell electrodes, andthe control circuit that is electrically coupled to the electroderecited in claim 19 is adapted to apply an AC voltage potential to thatelectrode.
 27. The apparatus of claim 26, wherein a root-means squarevalue of the AC voltage potential is greater than a magnitude of the DCvoltage.
 28. The apparatus of claim 19, wherein the apparatus comprisesa hand-held spray device, which comprises: a spray nozzle coupled in theliquid flow path; a pump coupled in the liquid flow path; a container inthe liquid flow path for containing liquid to be dispensed by thenozzle; and a power source electrically connected to the controlcircuit.
 29. The apparatus of claim 19, wherein the apparatus comprisesa mobile floor surface cleaner, which carries the liquid flow path, theliquid dispenser, the electrode and the control circuit and furthercomprises: a container in the liquid flow path for containing liquid tobe dispensed by the liquid dispenser; at least one wheel configured tomove the cleaner over a surface; a pump coupled in the liquid flow path;and a motor coupled to drive the at least one wheel.
 30. A methodcomprising: applying a voltage to an electrode on an apparatus, thevoltage having a sinusoidal waveform comprising at least one step on anedge of the waveform, wherein each step comprises a local peak; andarranging the apparatus to generate an alternating electric fieldbetween the electrode and a surface or volume of space in response tothe applied voltage, wherein the apparatus lacks a corresponding returnelectrode representing a circuit ground for the electrode on theapparatus.
 31. The method of claim 30, further comprising: dispensing aliquid from the apparatus to the surface or volume of space so as tocreate an electrically conductive path by the liquid from the apparatusto the surface or volume of space; and during the step of dispensing,applying the voltage to the electrode to generate the electric fieldalong the electrically conductive path
 32. The method of claim 31,further comprising: electrolyzing a source liquid prior to the step ofdispensing to produce an anolyte liquid and a catholyte liquid that areseparated by an ion exchange membrane; and wherein the step ofdispensing comprises dispensing at least one of the anolyte liquid, thecatholyte liquid or a combination of the anolyte liquid with thecatholyte liquid from the apparatus.
 33. The method of claim 31, furthercomprising: suspending at least one microorganism from the surface withcharged nanobubbles delivered to the surface by the liquid, wherein theelectric field is sufficient to destroy at least one microorganism fromthe surface or in the volume of space.
 34. The method of claim 30,wherein the electric field is sufficient to destroy at least onemicroorganism from the surface or in the volume of space.
 35. The methodof claim 30, further comprising: suspending at least one microorganismfrom the surface by at least one of the group consisting of chargednanobubbles delivered to the surface by the liquid, a detergent, ormechanical action on the surface.
 36. The method of claim 30, whereinthe electric field is sufficient to cause irreversible electroporationof at least one microorganism on the surface or in the volume of space.37. The method of claim 30, wherein the apparatus comprises a hand-heldspray device or a wheeled mobile surface cleaner.
 38. The method ofclaim 30, wherein: the waveform has a frequency in a range of 28 KHz to40 KHz; and the voltage is in a range selected 50 Volts rms to 1000Volts rms.
 39. The method of claim 30, further comprising: electrolyzinga source liquid by applying a DC voltage to an electrolysis cell priorto the step of dispensing to produce an anolyte liquid and a catholyteliquid that are separated by an ion exchange membrane; and applying anAC voltage potential to the electrode, which is in electrical contactwith at least one of the anolyte, the catholyte, or a combination of theanolyte and the catholyte so as to generate the alternative electricfield.